Coordination Chemistry Reviews 293–294 (2015) 19–47

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

On the design of highly luminescent lanthanide complexes

Jean-Claude G. Bünzli a,b,∗
a
École Polytechnique Fédérale de Lausanne, Institut des Sciences Chimiques et Ingénierie, BCH 1402, CH-1015 Lausanne, Switzerland
b
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People’s Republic of China

Contents

1. Lanthanide luminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.1. Historical landmarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.2. Mechanisms of lanthanide luminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.2.1. Interconfigurational 4fn ↔4fn 5d1 transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.2.2. Charge-transfer transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.2.3. Intraconfigurational f–f transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3. Applications of lanthanide luminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2. Optimization of energy transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1. Stating the problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2. Theoretical modelling for EuIII complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.3. Role of triplet states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.4. Role of singlet states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.5. Role of charge-transfer states and photo-induced electron transfers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.5.1. Intraligand charge transfer states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.5.2. Ligand-to-metal charge-transfer states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.5.3. Metal-to-ligand charge-transfer states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.5.4. Relationship with redox properties (photoinduced electron transfers). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3. Minimizing radiationless vibrational de-activation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.1. Quenching by OH vibrations and hydration number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2. Influence of weak intermolecular interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.3. Vibrational quenching of NIR-luminescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.4. Revisiting the energy gap law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4. Can the radiative lifetime be tuned? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5. Highly luminescent LnIII -containing coordination compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.1. Visible-emitting ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.2. Near-infrared emitting ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
5.3. Dual emissive ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

a r t i c l e i n f o a b s t r a c t

Article history: Presently, phosphors and luminescent materials for lighting, telecommunications, displays, security inks
Received 4 September 2014 and marking, as well as for probes in biosciences represent one third of the total value of the lanthanides
Received in revised form 20 October 2014 used worldwide. If optical glasses and laser materials are added, this figure is close to 40%, explaining the
Accepted 30 October 2014
large interest that the scientific community is devoting to such materials. The present review focuses on
Available online 7 November 2014
the design of highly luminescent lanthanide complexes and discusses all aspects needing optimization.
Reference is made to the mastering of the various energy migration processes in luminescence sensi-
Keywords:
tization by organic ligands, to minimizing non-radiative deactivation mechanisms, as well as to other
Lanthanide
Luminescence
parameters such as the radiative lifetime, the refractive index, and the benefit of inserting luminescent

∗ Correspondence to: École Polytechnique Fédérale de Lausanne, Institut des Sciences Chimiques et Ingénierie, BCH 1402, CH-1015 Lausanne, Switzerland.
E-mail address: jean-claude.bunzli@epfl.ch

http://dx.doi.org/10.1016/j.ccr.2014.10.013
0010-8545/© 2014 Elsevier B.V. All rights reserved.
20 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
Design complexes into inorganic-hybrid structures. Comparative tables list the most luminescent complexes
Energy transfer emitting in the visible and near-infrared ranges and the best chromophores are pointed out.
Radiationless transitions
Quantum yield
Lifetime
Radiative lifetime
Luminescent complexes
Model calculations
1. Lanthanide luminescence
A search for lanthanide luminescence and associated terms in
any bibliographic database or web search engine will typically
return tens of thousands of articles, pointing to the popularity
of the field. Indeed, applications as diverse as lighting, telecom-
munications, road marking, or immunoassays rely on lanthanide
luminescence. In this review article, we intend to highlight salient
features of the emission of light by lanthanide coordination com-
pounds, with special emphasis on the requirements needed to
design highly emissive materials. It is noteworthy that detection
of lanthanide-containing single particle or molecule is at hand,
using relatively simple instrumentation; in particular, it has been
demonstrated for Ln-doped oxide nanoparticles [1], upconverting
nanocrystals [2,3], and, quite recently, for an europium chelate
[4]. This is useful for multicolour barcoding [5,6] and in biologi-
cal sensing and imaging: for instance, a single nanoparticle can be
used to monitor the production of reactive oxygen species inside
live cells [7].
Emission of light by chemical compounds or materials stems
from two different mechanisms: incandescence, or black-body
emission, which does not depend on the chemical nature of the
material but only on its temperature, and luminescence or “cold
light emission” [8] that involves quantified energy levels in the
sample. Luminescence can be excited in different ways and specific
terms are used accordingly; to name but a few: thermolumines-
cence is consecutive to heating of the sample, liberating energy
trapped in defects; photoluminescence results when the sample
is irradiated with photons; electroluminescence is produced upon
excitation of the sample in an electric discharge or in an elec-
tric field; chemiluminescence (bioluminescence) arises from the
energy released by a chemical (biological) reaction. In the follow-
ing, however, we exclusively concentrate on photoluminescence,
abbreviated luminescence, and on f–f transitions. Depending on the
emission mechanism, luminescence can be divided into two pro-
cesses: fluorescence is defined as a fast, spin-allowed phenomenon
while phosphorescence is a slow, spin-forbidden emission. Lan-
thanide ions display fluorescence, phosphorescence or, often, both
types of luminescence [9].
1.1. Historical landmarks
As for many other elements, spectroscopy, particularly atomic
spectroscopy but, also, luminescence of salts and oxides, has played
a major role in the discovery and precise identification of the
series of elements named lanthanoids or lanthanides (Ln, Z = 57–71)
between 1803 (cerium) and 1907 (lutetium; promethium was arti-
ficially synthesized in 1947) [10]. The spectroscopic properties of
lanthanide ions are unique due to the radial extension of the 4f
orbitals being smaller than the expansion of filled 5s2 and 5p6
sub-shells. This feature confers Ln ions a special status in photon-
ics with respect to light generation, amplification, and conversion
[11]. In our opinion, the field has been shaped by eight important
discoveries that are briefly described in this section.
(i) The Auer light. The first industrial application of lanthanides
has taken advantage of cerium emission when Carl Auer von
© 2014 Elsevier B.V. All rights reserved.
Welsbach demonstrated in 1891 that addition of 1% CeO2
to ThO2 leads to much brighter white light emission upon
heating; he therefore created the incandescent gas mantle,
also known as the Auer light. In fact since visible emission
is larger than expected from the black body curve in these
mantles, while infrared emission is minimized, it seems that
thermoluminescence is operating in addition to incandes-
cence, so that the resulting complex phenomenon is termed
candoluminescence. Modern versions of these mantles are
still in use today.
(ii) The red phosphor. Another important discovery was made at
the turn of the 20th century when Georges Urbain studied
the luminescence of EuIII ions diluted in various matrices
[12]. This eventually led to the discovery of the extraordinary
bright, orange-red emitting phosphor Y2 O3 :Eu (4–6 mol%)
that is close to the ideal prime-colour red-emitter. This phos-
phor, with quantum yield close to 1 [13], is a real nature’s
gift. It has been used in fluorescent lamps and cathode-ray
tubes since the early 1960s and is still providing brilliant red
colour for light-emitting diodes, displays of all kind, includ-
ing flat-panel televisions, despite the large variety of potential
substitute materials tested so far, but with limited success.
(iii) Solving the puzzle of lanthanide optical spectra. In 1937, J.H. Van
Vleck deciphered the long intriguing and obscure nature of
the sharp optical transitions observed for most of the trivalent
lanthanide ions [14]. He stated that these transitions are for-
bidden and postulated that the most intense ones are electric
dipole in nature and caused by a “distortion of the elec-
tronic motion by crystalline fields”. He also established that
this “distortion” arises only if the ligand field does not have
an inversion centre, otherwise orbital mixing cannot occur.
Probabilities for quadrupolar, magnetic dipole, and electric
dipole transitions were estimated. Finally, Van Vleck pointed
out that interaction between vibrations and electron motion
results in additional vibronic lines in the spectra and/or in
broadening of some lines. In a way, this contribution can be
compared with the order brought in the forest of elements by
the Periodic Table and it paved the way for Diecke’s diagram,
ligand-field modelling, and Judd–Ofelt theory.
(iv) The antenna effect. Molar absorption coefficients (ε) of
trivalent lanthanide ions are small, usually in the range
0.1–10 M−1 cm−1 so that even if quantum yields (Q)
reach sizeable values, the overall luminosity (L = ε × Q) of
LnIII -containing luminescent compounds remains small (typ-
ically  10 M−1 cm−1 ) if samples are excited into the f–f
transitions. In 1942, S.I. Weissman [15] discovered that light
emission in lanthanide complexes with organic ligands can
also be triggered when excitation is performed into the ligand
electronic levels. Energy is then funnelled onto the metal ion
excited states by intramolecular energy transfer. The energy
transfer mechanism is highly complex and will be dealt with
in details in Section 2. This finding, usually referred to as the
antenna effect or luminescence sensitization, proved to have
a major impact on the design of Ln-containing luminescent
compounds and materials since luminosity can now easily
reach 104 –105 M−1 cm−1 , being essentially determined by the
molar absorption coefficients of the surrounding ligands.
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
(v) The Judd–Ofelt theory. In 1962, two authors, B.R. Judd [16]
and G.S. Ofelt [17] independently submitted, within a month,
two manuscripts describing a similar model for the empiri-
cal parameterization of the intensities of lanthanide optical
spectra. The theory considers a free ion with a well-defined
single ground-state electronic configuration perturbed by a
static electric ligand-field (LF) generated by the chemical
environment of the ion. While purely magnetic dipole tran-
sitions can be calculated in a straightforward way, electric
dipole intensities are fitted to a set of three “Judd–Ofelt” (JO)
parameters, ˝2 , ˝4 , and ˝6 that allow comparing covalence
contributions to the Ln-ligand bonds. Several assumptions are
assumed to derive expressions leading to the determination
of these parameters from 4f–4f absorption spectra: (i) elec-
tronic states are completely degenerate in quantum number
J, (ii) the energy difference between the 4fn and 4fn−1 5d1 elec-
tronic configurations is equal to the difference in the average
energies of the 4f and 5d sub-shells, (iii) all LF sub-levels are
equally populated, and (iv) the material is isotropic. Despite
all hypotheses involved, the theory is remarkably accurate,
except for some ions, such a TbIII for instance. Once JO param-
eters are known, transition probabilities between two states
with J and J quantum numbers, AJ ,J , can be evaluated, as
well as the radiative lifetime  rad = 1/krad (vide infra) and the
branching ratio ˇJ ,J [18].
(vi) Upconversion. Emission of light in compounds and materi-
als usually follows Stokes’ law which states that emitted
photons have a smaller energy than excitation photons. In
a way this is equivalent to say that the efficiency of the
luminescence process cannot be larger than one. In 1966,
F. Auzel suggested that energy transfer can occur between
neighbouring Ln ions that are both in their excited states
[19]; this sequential energy transfer is more efficient than
excited-state absorption (or 2-step absorption) and rep-
resents therefore a major mechanism in upconversion, a
process in which two (or more) low-energy photons are
combined resulting in the emission of one higher-energy
photon. Initially developed for infrared quantum counters,
upconverting materials were soon found to have other appli-
cations. In particular, ytterbium, which has a relatively large
absorption coefficient at 980 nm (around 10–12 M−1 cm−1 )
is an ideal sensitizer for upconverted luminescence of ErIII
and HoIII (green and red) or TmIII (UV and blue) [20]. YbIII -
and LnIII -doped materials (Ln = Ho, Er, Tm) have been there-
fore used in the manufacture of lasers and, also, in security
inks and markers. Present developments include upconvert-
ing nanoparticles (or nanophosphors, UCNPs) which are very
useful in bioanalyses [21], bioimaging [22], drug release [23],
barcodes and counterfeiting tags [5], as well as, possibly,
solar energy conversion [11,24]. The opposite phenomenon
to upconversion, downconversion (or quantum cutting) in
which one high-energy photon is transformed into two
lower-energy ones, was documented in 1997 [25] and has
potential applications in lighting and energy conversion
processes.
(vii) Time-resolved luminescence immunoassays. At the beginning of
the 1980s, an original idea came from the city where the first
rare-earth element, yttrium, was identified, Turku in Finland:
E. Soini and I. Hemmilä proposed replacing radioactive-
based immunoassays by time-resolved luminescent assays
using a lanthanide chelate conjugated to some specific anti-
body as bioprobe [26]. Not only are these analyses taking
advantage of intramolecular energy transfer to excite the
metal ion but, also, they fully exploit specific properties of
lanthanide luminescence: wavelength discrimination thanks
to large ligand-induced Stokes’ shifts, time discrimination,
21
resulting in much improved signal-to-noise ratios, and, last
but not least, little or no photobleaching. In addition, cum-
bersome elimination of (low activity) radioactive wastes
is avoided. Detection limits in the fM range are attain-
able. The technology that involves a two-step protocol, met
immediate success [27] and was later simplified thanks to
Förster resonant energy transfer allowing one-step homo-
geneous assays [28]; nowadays, immunoassays based on
lanthanide luminescence are ubiquitous in medical labora-
tories. Furthermore a logical extension is to apply similar
protocols to bioimaging thanks to time-resolved lumines-
cence microscopy [29,30].
(viii) Erbium-doped fibre amplifier. The ErIII ion has a rich elec-
tronic configuration with many equally separated levels,
allowing the design of multi-level lasers in addition to its
role in upconversion. In 1986, the first tuneable continuous-
wave and Q-switched erbium-doped fibre laser was described
[31] which, combined with the earlier work of Digonnet
and Shaw on tuneable optical fibre couplers [32], led to
the development of erbium-doped fibre amplifiers (EDFAs)
and planar waveguides together with associated optical-fibre
telecommunication networks [33]. In EDFAs, ErIII is excited
either at 980 nm, on the 4 I11/2 level, or at 1480 nm, on a
metastable ligand-field sub-level of the 4 I13/2 electronic level.
This results in a laser effect with emission in the range
1530–1550 nm depending on the fine-tuning of the materi-
als into which ErIII is doped. The 980-nm band has higher
absorption cross-section, so it is generally used when low-
noise performances are required; the transition is narrow
and therefore wavelength-stabilized laser sources are needed
to pump energy into it. The 1480-nm band features a lower
absorption cross-section but is broader, which makes it ideal
for high-power amplifiers. Many EDFAs use a combination
of both pump wavelengths. Owing to restrictions imposed
by silica-based EDFAs, namely low absorption cross-section
of ErIII and concentration quenching preventing the use of
metal-ion concentrations larger than 1020 ions per cm3 , alter-
native matrices and materials are presently investigated.
This includes co-doping YbIII for larger cross-sections and
designing polymer fibres containing antenna ligands, a dif-
ficult task since C H vibrations have to be eliminated as far
as possible because they easily quench ErIII luminescence;
important progress has recently been made towards this goal
[34]. Other extensions feature the integration of both ErIII -
doped waveguide amplifier and laser on a single chip [35]
and the fabrication of microstructures with very high gain
[36].
1.2. Mechanisms of lanthanide luminescence
The electronic configuration of trivalent lanthanide ions is
[Xe]4f n (n = 0–14); some divalent ions have similar f-electronic con-
figuration [Xe]4f n + 1 (n = 3, 5, 6, 9, 12, 13; Ln = Nd, Sm, Eu, Dy, Tm,
Yb), while the electronic configuration of the others is [Xe]4f n 5d1
(n = 0, 1, 2, 7, 8, 10, 11, 14; Ln = La, Ce, Pr, Gd, Tb, Ho, Er, Lu).
The 4f n configurations generate a wealth of electronic levels char-
acterized by three quantum numbers, S, L, and J, and that are
further split by weak ligand field effects, on the order of 102 cm−1 ,
since the 4f orbitals are shielded: for instance, EuIII possesses 3003
ligand-field (or Stark) sub-levels. When d-orbitals are implied,
the ligand field generated by the surrounding ligands is much
larger (103 –104 cm−1 ). The arduous task of finding, calculating and
assigning energy levels in transition metal containing compounds
started to be undertaken in the 1940s, particularly by Racah, and
enabled quantitative fits of the LF sub-levels for the entire lan-
thanide series to be performed thanks to the work of B.G. Wybourne
22 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
48
λ / nm
225 250 300
44
ε / 102 M-1cm-1
E / 103 cm-1
4
2 40
0
48 44 40 36 32
E / 103 cm-1
2 7/2
0 5/2
Fig. 1. Left: absorption spectrum of [Ce(H2 O)9 ]3+ doped into lanthanum ethylsul-
fate; redrawn from Ref. [43]. Right: corresponding energy scheme.
[37]. The first synopsis of the 4fn energy levels of all trivalent lan-
thanides doped in various crystals and spanning the entire UV,
visible and NIR spectral ranges was given by G.H. Dieke [38]. The
“Dieke diagram” has now been expanded to include higher-energy
levels [39]. In addition, theoretical work by Judd and Ofelt [40]
allowed describing, comparing, and predicting electronic spectra of
lanthanide ions in isotropic crystals, glasses, and coordination com-
pounds. Presently, the spectroscopy of lanthanide ions with respect
to both energy levels and transition intensities is fairly well under-
stood and will not be developed here. The reader is referred to one
of the several review articles dealing with the subject [9,18,40,41].
There are three types of optical transitions in lanthanide com-
pounds: allowed f↔d and charge-transfer transitions, as well as
forbidden f↔f transitions.
1.2.1. Interconfigurational 4fn ↔4fn 5d1 transitions
For the free ions (LnIII or LnII ), these transitions lie usually in
the VUV or UV spectral ranges. Due to the extension of the 5d
orbitals, ligand-field splitting can however push some of the Stark
sub-levels deep into the visible; this is particularly true for CeIII
and EuII compounds. Spectra are difficult to interpret in that a good
deal of their intensity rests in vibronic components and both 4f and
5d LF splitting have to be taken into account. As a consequence,
f↔d transitions are broad, intense, energy-tuneable, and feature
large Stokes’ shifts while the 4fn 5d1 excited state lifetime is short,
typically in the 10–100 ns range. As an example, the absorption
spectrum of [Ce(H2 O)9 ]3+ in water (idealized D3h symmetry) is
displayed in Fig. 1 along with the corresponding energy scheme,
exemplifying the (J + 1/2) ligand-field splitting of the d- and f-
orbitals. Note the scale change due to the much larger 5d-splitting
compared with 4f-splitting. At low temperature, two luminescence
bands are observed at 30 000 and 32 000 cm−1 for [Ce(H2 O)9 ]3+
doped into lanthanum ethylsulfate [42], assigned to emission from
2D 2
3/2 to F7/2,5/2 . The corresponding lifetime in water is 45 ns [43].
The tuneability of d–f luminescence is demonstrated in a series
of EuII -doped inorganic matrices in which emission maxima range
from 330 to 520 nm, albeit thanks to some mixing with conduction-
band states of the host material [44]. When sulfides are used as
matrices, the emission wavelength can even be extended to 650 nm
[45]. The versatility of such materials is demonstrated in Fig. 2 in
which the coordinates of several EuII - or CeIII -doped thiosilicates
are reported on the CIE (Commission Internationale de l’Éclairage)
trichromatic diagram. The TbIII ion (4f8 ) represents an interest-
ing case. Since the number of valence electrons is larger than 7,
both low- and high-spin 4f7 5d1 electronic configurations can be
generated depending on the surrounding ligands. The high-spin
configuration (9 DJ ) has lower energy than the low-spin one (7 DJ )
2D
5/2
2D
3/2
2F
2F
Fig. 2. Emission colours of EuII - and CeIII -doped thiosilicates (1 mol%).
Reproduced with permission from Ref. [45]; © 2010 MDPI publishers.
so that 9 DJ ↔7 F6 transitions are spin forbidden while those between
7 D and 7 F are spin-allowed. Therefore if TbIII is coordinated to soft
J 6
nitrogen ligands, the latter transitions can be red-shifted as low as
31 000 cm−1 . For a listing of 5d1 4fn−1 ←4fn transitions of LnIII ions
(Ln = La Dy, Er Yb) into inorganic matrices, see refs. [46,47].
1.2.2. Charge-transfer transitions
Ligand-to-metal charge-transfer (LMCT) transitions are essen-
tial in sensitizing the luminescence of lanthanide-containing
inorganic phosphors but as for 5d–4f transitions, their energy is
large and corresponding bands usually appear in the VUV and UV
ranges [46]. Easily reducible trivalent ions such as SmIII , EuIII , and
YbIII have the lowest LCMT transitions: 200–250 nm for 2p(O)→4fn
charge transfer [47], but this can be modulated by the nature of
coordinated ligands and, in the case of EuIII , transitions with ener-
gies as low as 20–25 000 cm−1 have been reported for dinuclear
complexes with calix[8]arene, with molar absorption coefficients
around 720–740 M−1 cm−1 . The presence of such a low-lying CT
state induces mixing with the 4f-states and results in larger oscil-
lator strengths for the 4f–4f transitions [48]. In the case of YbIII , the
LMCT state has energy blue-shifted by ∼5000 cm−1 compared with
EuIII , which approximately corresponds to the difference in normal
reduction potentials of these ions (∼0.7 eV, 5600 cm−1 ). The role of
LMCT states in sensitizing or quenching LnIII luminescence will be
discussed in Section 2.5, but we would like to mention here that a
few CeIV compounds emit light upon excitation into O(2p)→Ce(4f)
CT transition, yielding a transient reduced CeIII species, e.g. the
Lindqvist polyoxolanthanate [Ce(W5 O18 )2 ]8− [49].
Metal-to-ligand charge-transfer (MLCT) states are very com-
mon in d-transition compounds but they are rarely observed
with lanthanides because they lie at very high energy, except for
CeIII which can easily be oxidized into Ce(IV): in tris(pyrazine-
2-carboxylato)cerium(III), a weak absorption band at 388 nm
observed in mixed CH3 CN/DMF solvent is thought to arise from
a MLCT transition from 4f1 to the ␲* orbital of the pyrazine-
2-carboxylate ligand, known as being an electron acceptor;
conversely, the weak blue-green luminescence exhibited by this
compound has been attributed to the MLCT state [50]. TbIII is also
a potential candidate for MLCT transitions.
1.2.3. Intraconfigurational f–f transitions
Description of the interaction between photons and matter
considers the former behaving as waves comprised of two perpen-
dicular fields, electric and magnetic, oscillating in time. When a
photon is absorbed, its energy is transferred to an electron which
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 23

Table 1
Selection rules and approximate relative intensities Irel for f–d and f–f transitions [53].

Transition Parity S |L| |J| Irel

ED, 4f–5d Opposite 0 ≤1a ≤1c 0.01–1

Forced ED, f–f Same 0 ≤6a (2,4,6 if L or L = 0) ≤6c (2,4,6 if J or J = 0) 10−4
MD, f–f Same 0 0 ≤1c 10−6
EQ Same 0 ≤2b ≤2d 10−10
ED vibr, f–f Same 0 ≤6a (2,4,6 if L or L = 0) ≤6c (2,4,6 if J or J = 0) 10−7 –10−10
a
L = 0↔L = 0 forbidden.
b
L = 0↔L = 0,1 forbidden.
c
J = 0↔J = 0 forbidden.
d
J = 0↔J = 0,1 forbidden.

is then lifted into an orbital with higher energy. The absorption is equation assumes that the absorption bands are symmetrical, i.e.
promoted by operators linked to the nature of light: the odd-parity either Gaussian or Lorentzian. If not, Eq. (3) has to be replaced with:
electric dipole (ED) operator, the even-parity magnetic dipole (MD)   
and electric quadrupole (EQ) operators. Laporte’s parity selection 1036 9n ε(˜)
D(exp) = · (2J + 1) · · d˜ (4)
rule states that levels with same parity cannot be connected by 108.9 · XA (n2 + 2)
2 ˜
electric dipole transitions; as a consequence f–f transitions are
forbidden by the ED mechanism. However, under the influence of As for absorption, emission of light through f–f transitions is
a ligand-field, non-centrosymmetric interactions result in the mix- achieved by either ED or MD mechanisms and the selection rules
ing of electronic states of opposite parity, which somewhat relaxes detailed in Table 1 apply. Important parameters characterizing the
the selection rules and the transitions become partially allowed; emission of light from an LnIII ion are the lifetime of the excited
they are called induced (or forced) electric dipole transitions. Some state  obs = 1/kobs and the quantum yield Q:
induced ED transitions are highly sensitive to minute changes in
the LnIII environment and are called hypersensitive (for a listing, number of emitted photons
Q = (5)
see [51]). number of absorbed photons
On the other hand, magnetic dipole transitions are allowed, but
their intensity is weak; in 4f–4f spectra however they frequently The quantum yield depends on the rate at which the excited
have intensity of the same order of magnitude as induced electric level is depopulated, kobs , and on the radiative rate krad :
dipole transitions. Quadrupolar transitions are also parity allowed,
but they are weak and have been rarely identified unambiguously. krad 
Ln
QLn = = obs (6)
Mathematical treatment of the parity mixing by the ligand-field kobs rad
perturbation leads to the selection rules for f–f transitions listed in
Table 1. Selection rules are derived under several hypotheses which where subscript and superscript “Ln” mean that excitation has been
are not always completely fulfilled in real compounds so that the performed directly into the 4f excited state and the quantity defined
terms “forbidden” and “allowed” transitions should be understood in Eq. (6) is called the intrinsic quantum yield (sometimes, inter-
as “low probability” and “high probability” transitions. According nal quantum efficiency). The rate constant kobs is the sum of the
to Judd–Ofelt theory the dipole strength in esu2 cm2 (=1036 debye2 ) rate constants characterizing the various radiative and radiation-
of an induced ED f–f transition between states  and   is given less deactivation processes:
by: 
i
kobs = krad + knr (7)

DED = e2 · ˝ · |
 ||U  ||  |2 (1) i

=2,4,6
Determination of QLnLn , which is difficult to measure experimen-

in which e is the electric charge of the electron, ˝ are phenomen- tally, is frequently conducted using Eq. (6), requiring evaluation of
ological Judd–Ofelt parameters, expressed in cm2 and calculated the radiative lifetime:
from the absorption spectrum ε(˜), and U are the irreducible ten- 2

sor forms of the ED operator. The bracketed expressions in Eq. (1) 1 644 ˜ 3 n(n2 + 2)
= krad = DED + n3 DMD (8)
are dimensionless doubly reduced matrix elements which are tab- rad 3h(2J + 1) 9
ulated [52] and independent of the ion environment.
Oscillator strengths for magnetic dipole transitions can be cal- Except in few cases, this calculation is not trivial and errors may
culated from the following equation where h is Planck’s constant: occur, including those pertaining to the hypotheses made within
Judd–Ofelt theory. In particular, it has been assumed that the emit-
 e·h
2 ting and receiving levels are (2J + 1)-fold degenerate or, if split by
DMD = · |
 ||L + 2S||  |2 (2) ligand-field effects, that all the sub-levels are equally populated.
4 ·  · me · c
This is obviously not true and in the case of TbIII and ErIII this may
The experimental dipole (or oscillator) strength is defined as: lead to errors up to 20–100%.
On the other hand, if the absorption spectrum corresponding
  
1036 9n to an emission spectrum is known, which may be the case when
D(exp) = · (2J + 1) · · ε(˜)d˜ (3) the luminescence transitions terminate onto the ground level, the
108.9 · ˜ mean · XA (n2 + 2)
2
radiative lifetime can be simply calculated from the following equa-
tion where NA is Avogadro’s number:
with XA being the fractional   of the initial state while
population
˜ mean is given by ˜ mean = ˜ · ε(˜)d˜/ ε(˜)d˜; (2J + 1) is the degen- 
1 8cn2 ˜ 2 (2J + 1)
eracy of the initial state and the expression involving the refractive = 2303 × ε(˜)d˜ (9)
index n is known as Lorentz’s local-field correction. The above rad NA (2J  + 1)
24 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

Table 2 telecommunications and laser materials. The best known laser

Experimental intrinsic quantum yields, observed and radiative lifetimes of
is the neodymium YAG laser emitting at 1.06 ␮m, which can be
M3 [Ln(dpa)3 ] (M = Na or Cs) samples in solution (0.1 M Tris–HCl, pH 7.4) and solid
state at 295 K; 2 are given between parentheses [56]. doubled (532 nm), tripled (355 nm), or quadrupled (266 nm) and
which is seen in uses as disparate as laser pointers, military target
Ln
Sample QLn /%  obs /ms  rad /msa
designation, rangefinders, and weapons, experimental setups for
(i) (ii) (iii) controlling nuclear fusion, or medicine, in oncology, ophthalmol-
−2
Eu, 1.8–3.7 × 10 M 41(2) 1.7(0.1) 4.1(3) 3.15 4.0 ogy or thermotherapy. Another well-established use of lanthanide
Eu, solid stateb 68(4) 1.8(0.1) 2.6(2) – 2.7 luminescence is in time-resolved bioanalyses and bioimaging. In
Tb, 2.0 × 10−2 M c
1.74(1) – 1.0 – parallel, security inks and counterfeiting tags are more and more
Tb, solid stateb 72(5) 1.36(2) 1.9(1) – – relying on lanthanide luminescence, particularly since the advent
Yb, 4.04 × 10−2 M c
2.23(1)d – – 1.31(2)
of UCNPs. Potential new applications include solar energy conver-
a
(i) experimental, Eq. (6), (ii) from JO theory, Eq. (8), (iii) from Eqs. (10) for Eu and sion [24], luminescence thermometry [59], damage and pressure
(9) for Yb.
b
sensors based on mechanoluminescence [60], optical refrigeration
Refractive index = 1.517.
c
Determination not feasible. for electronic devices [61], and quantum information processing
d
In ␮s. [62].
Until the turn of the 20th century, the search for lanthanide-
containing luminescent materials has essentially proceeded
In the special case of EuIII for which the 5 D0 →7 F1 transition has through a trial-and-error strategy with only some semi-
pure magnetic origin [54], a convenient simplified equation can be quantitative concepts and rules to guide the investigators. But the
derived [55]: development of powerful methods of calculation with good param-
1
I  eter sets for the 4f orbitals, the re-visitation of some initial concepts
tot
= AMD,0 · n3 (10) underlying lanthanide spectroscopy, as well as systematic stud-
rad IMD
ies of the wealth of quantitative quantum yield and lifetime data
with AMD,0 being equal to 14.65 s−1 and (Itot /IMD ) being the ratio reported in the literature are slowly changing the attitude of the
of the total integrated emission intensity from the Eu(5 D0 ) level to scientists and engineers so that the design of highly luminescent
the 7 FJ manifold (J = 0–6), to the integrated intensity of the 5 D0 →7 F1 materials and probes is becoming more programmed. Some of the
transition. challenges and potential answers are described in the next section
Examples of radiative lifetime calculations based on the vari- but one always has to keep in mind that each application has special
ous equations described above are collected in Table 2. The limit of requirements and that each lanthanide ion is a special case!
Judd–Ofelt approach is evident for TbIII (error > 100%). On the other
hand, Eqs. (9) and (10) yield trustworthy results; in particular, the
radiative lifetime for the YbIII complex is in line with those reported 2. Optimization of energy transfer
for other coordination environments, 1.2 ms for [Yb(dtpa)]2− [56]
and 0.7–0.75 ms for complexes with benzoxazole-substituted 8- In this section, we focus exclusively on f–f luminescence and
hydroxy-quinolinates [57]. decipher the various parameters to be optimized upon the assump-
The radiative lifetime depends on the LnIII ion, the specific tion that luminescence sensitization is achieved by the chemical
excited state level giving rise to luminescence, the chemical envi- environment into which the emissive ion is embedded, inorganic
ronment of the metal ion, and the refractive index of the medium; or organic.
it can therefore vary considerably even for a given emitting level,
e.g. between <1 and 14 ms for Eu(5 D0 ).
2.1. Stating the problem
1.3. Applications of lanthanide luminescence
A highly simplified schematic diagram of energy transfer pro-
According to various reports and estimates, luminescent mate- cesses occurring in a luminescent lanthanide material is presented
rials account for about one third (∼1.5–2 billion US$ in 2012) of in Fig. 3. In a first step, the surrounding ligand(s) absorb light and
the commercial value of the rare earths extracted annually, while reach an excited state that is often a singlet excited state in com-
representing ∼7–8% of their tonnage (8–9000 metric t equivalent pounds with organic ligands. In a second, composite step, energy
rare-earth oxides in 2012). A characteristic is that these high value- is funnelled onto a donor state (for example a triplet state) with,
added materials only constitute a fraction of the weight of the ideally, a relatively long lifetime and is then transferred onto one
products they valorize. Typically, a fluorescent bulb contains less or several LnIII excited states. Finally, after suitable internal conver-
than 1 g of Ln phosphors, a LED lamp or a cell phone has less than sion to an emissive state, metal-centred luminescence is emitted.
0.1 g of rare earths, and a luminescent immunoassay frequently Consequently, a new quantum yield has to be defined, different
from QLnLn , the overall quantum yield Q L :
requires less than 10 ␮g of luminescent lanthanide. Both d–f and Ln
f–f luminescence have found applications. The former in scintilla-
tors for the detection of ionizing radiation and in white-light LEDs L ILn (E)
QLn = (11)
under the form of a yellow phosphor, Y3 Al5 O12 :CeIII (0.033 mol%). IL (A)
Long-persistence materials that feature light emission up to several
hours after excitation commonly rely on broad d–f emission from where ILn (E) represents the number of photons emitted by the
EuII [58]. They are seen in emergency and safety signals, includ- metal ion and IL (A) the number of photons absorbed by the
ing road marking, in dials and displays, and textile printing; more ligand. This quantum yield can at most be equal to the intrinsic
recently they have been introduced into alternative-current LEDs quantum yield QLn Ln described in Eq. (6). Absorption being ligand-

and they are tested for applications in bioimaging and energy stor-
age.
Luminescence arising from f–f transitions is the basis of
numerous applications [11]. Previously mentioned lamp and
display phosphors constitute the largest category, followed by
centred while emission is Ln-centred, there is usually a large
wavelength shift between absorption and emission, the so-called
ligand-induced Stokes’ shift (or Richardson’s shift [53]), not to be
confused with the frequently misused Stokes’ shift (which is very
small for LnIII ions, due to the inner nature of 4f orbitals). The
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
Fig. 3. Simplified scheme depicting the antenna effect, with associated photophys-
ical parameters; right: rule of thumb for minimizing vibrational quenching. Key:
A = absorption, E = emission, D = donor state.
sensitization efficiency, which characterizes the set ligand(s)/LnIII
ion can now be defined as:
L
QLn
sens = Ln
(12)
QLn
Therefore the following experimental photophysical parame-
ters are needed to fully characterize the process: QLn Ln , Q L ,  , ,
Ln obs rad
and
sens .
From a conceptual point of view, maximizing the luminos-
ity of lanthanide-containing materials is fairly straightforward: (i)
the metal-ion surrounding must be highly absorbing with large
molar absorption coefficients, (ii) losses in energy transfers have
to be minimized and (iii) radiationless deactivation of the excited
metal ion should be minimized. From a practical viewpoint, how-
ever, the situation is far from being simple. The ligand-to-LnIII
energy transfer process is very complicated in that it may involve
several different mechanisms, exchange, dipolar-dipolar, dipolar-
multipolar, as well as several electronic levels, both from the
ligand(s) and from the metal ion. Nevertheless, on can say that,
overall, the sensitization process starts to be well mastered and
many highly luminescent complexes and materials have been
reported during the past decades. Regarding radiationless deactiva-
tion, the experimental command on this aspect is more complicated
because not only vibrations intervene but, also, back energy trans-
fer processes as well as quenching by charge-transfer states that are
not always easy to identify. The problem of vibrational deactivation
is particularly acute for ions emitting in the red and near-infrared
since the energy difference between the emissive and receiving
LnIII states can easily be bridged by high-energy vibrations (O H,
N H, C H, C O, etc.) and their overtones. Finally, the influence
of the polarizability of Ln-ligand bonds and of the refractive index
on the radiative lifetime (see Eqs. (8)–(10)) is only qualitatively
understood [63].
Nature of the donor state(s). The overall energy migration paths
in the complex represent a kinetic scheme and what has really to be
maximized are the rates of transfers between the initially excited
and the donor (D) ligand state(s), as well as between D and the
LnIII levels. Therefore it is desirable that D is long-lived and conse-
quently, triplet states (3 T, 3 MLCT) are often more likely to be major
actors in the process than singlet states. Triplet states usually trans-
fer energy through an exchange mechanism, while singlet states
25
(1 S) operate via dipolar-multipolar interactions. This does not mean
that singlet states do not contribute to the energy transfer process
(see Section 2.4): their importance has been recognized as soon
as 1969, particularly for TbIII sensitization when the ligand triplet
state is lower than the emissive 5 D4 level [64]. As a consequence,
the scheme of Fig. 3 is oversimplified and in reality one should take
into account more than one donor state. Other important levels are
charge-transfer states, either internal to the ligand (e.g. 1 ILCT in
push–pull ligands) or characteristic of the complex, LMCT or MLCT
states. Internal charge-transfer states may serve as energy relay in a
complex cascade of energy transfers [65]. They are often mixed with
singlet states, rendering interpretation of singlet-state excitation
delicate; the same hold for 1 LMCT states [66]. Moreover, in hete-
rometallic edifices featuring both d- and f-transition metal ions,
d levels and 1.3 MLCT states can be convenient feeding levels for
LnIII excitation [67,68]. Finally, in 4f–4f heterometallic compounds,
very efficient transfers between f-levels are operative which can be
exploited to excite a given LnIII ion; examples are TbIII -to-EuIII and
YbIII -to-LnIII (Ln = Ho, Er, Tm) transfers. One important point to real-
ize is that most discussions about energy transfer processes usually
consider energy levels of one ligand, whereas wavefunctions of the
entire complex edifice should be taken into account.
Radiationless de-activation processes. Since they open new routes
for de-exciting the metal ion, these processes can be recognized
by their influence on the excited-state lifetime, which is short-
ened. Both vibrations and photo-induced electron transfers being
temperature-dependent, dependence of  obs on temperature is also
diagnostic of their presence. The right-hand side of Fig. 3 depicts
de-activation through vibrations and their overtones. The smaller
the number of phonons needed to bridge the energy gap, the most
efficient is the luminescence quenching and as a rule of thumb, and
ideally, the chemical environment of the emissive metal ion should
be devoid of vibrations with energy larger than 1/6 of the energy
gap. For NIR-emitting ion, this requirement extends to the second
coordination sphere as well. To avoid quenching by charge-transfer
states, the only possibility is to modify the metal-ion coordina-
tion environment in such a way that the energy of the CT state is
increased largely above the emissive state of the metal ion, which
requires chemical modification of the ligand(s).
2.2. Theoretical modelling for EuIII complexes
Luminescent compounds containing EuIII ions are among the
most studied because of the intense red emission of this ion. From
a theoretical point of view this ion is also interesting because it
has non-degenerate ground (7 F0 ) and main emissive (5 D0 ) states.
On the other hand, its luminescence is sensitive to the influence of
LMCT states and it presents somewhat uncommon spectroscopic
features: (i) the first excited spin-orbit level, 7 F1 , lies only about
300 cm−1 above the ground state, so that at room temperature its
population is around 25–30% [54]; this is important because while
the 5 D0 ←7 F0 transition is highly forbidden, selection rules on J
point to 5 D0 ←7 F1 being MD allowed; (ii) moreover the 5 D1 excited
state is located a mere 1700 cm−1 above 5 D0 , so that it represents
an important receiving state in the energy transfer process, since
both 5 D1 ←7 F0 and 5 D1 ←7 F1 are MD allowed. Theoretical 3-step
modelling of the intricate energy transfers in EuIII complexes with
organic ligands has been initially proposed by G.F. de Sá et al. [69]
and further refined by R.O. Freire et al. [70], who designed a friendly
user computer package. The model consists in three steps and deals
essentially with EuIII complexes with organic ligands, but it will
certainly be extended to other ions in the future since one example
already exists for its application to a SmIII dinuclear helicate [71].
Step 1. The geometry of the complex is optimized within the
frame of the AM1 semi-empirical molecular orbital model. The
26 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

Fig. 4. (Left) Partial energy diagram showing electronic levels implied in energy transfer and relevant parameters. (Middle) Overlap between ligand emission and LnIII
absorption spectra. (Right) Definition of the parameters needed for the kinetic model.
Reprinted from Ref. [51].

bonding in lanthanide complexes having predominantly elec- integral JDA between the emission spectrum of the donor (ligand)
trostatic character, it is simulated within a central-potential and the absorption spectrum of the acceptor (EuIII ion) and (ii)
model, known as the Sparkle model. Suitable parameterization the distance between the donor and the acceptor, rDA , according
of Sparkle/AM1 with Gaussian functions has been achieved by to an exponentially decreasing function, e−ˇ·rDA . In the model it
reproducing known structures of several EuIII complexes [69,72], is expressed by the following equation:
and has then been rapidly extended to other LnIII ions; presently, 4
parameters are available for the entire series, from LaIII to LuIII [73]. 8 e2
4f |L
F
˛ J  ||S||˛J
ex 2
WET =
Other versions of the Sparkle model such as Sparkle/PM7 [74] or 3 (2J + 1)G · r 4
DA
Sparkle/RM1 for larger molecules, or even metal-organic frame-  2
   
 
works [75], have been tested satisfyingly, although Sparkle/AM1
tends to describe best the organic part of the complexes [76]. × 
ϕ| Z (k) sm (k)|ϕ  (15)
 
Step 2 implies calculating the energy and transition moments of m k

the ligand excited states with the INDO/S-CI model implemented

in the ZINDO program. The sparkle is replaced by a +3e point
 r 3.5
0

4f |L = (16)
charge to match the LnIII charge and despite this purely ionic model rDA
excluding any covalent contribution to the ligand-metal bonding,
4
calculated and experimental electronic spectra are in satisfying where
4f |L is a distance-dependent radial overlap where , the
agreement. Other authors have relied on more sophisticated meth- radial overlap integral between the 4f orbitals and the valence
ods for calculating triplet-state energies in complexes, for instance orbitals of the ligating atoms, is about 0.05, and r0 is the short-
ab-initio complete active space self-consistent field (CASSF) or est Ln X ligating distance [79]; G is the degeneracy of the
time-dependent density functional calculations (TD-DFT) [77,78]. ligand ground state, J is the total angular momentum quan-
The final step 3 is devoted to developing a kinetic model including tum number of the LnIII ion, S is the spin operator of the LnIII
analytical expressions for the transfer rates. The rates of transfer, ion, z is the z-component of the ED operator, sm (m = 0,±1) is
WET , are expressed within the general theory proposed by Fermi a spherical component of the spin operator (the index k runs
assuming the validity of Born–Oppenheimer approximation: over the electrons of the ligand). Note that the e−ˇ·rDA distance
 is contained
dependence  in
 the right-hand summation in which
2 the ϕ  k z (k)sm (k) ϕ matrix elements are calculated by
WET = |
˛ J  ϕ|H|˛Jϕ |2 · F (13) INDO/S-CI method. The rDA distance is in fact the distance from

the LnIII ion to the region of the ligand in which the donor state is
In this expression,  = h/2, with h being Planck’s constant, H is the
localized; it is evaluated with the following equation in which ci
Hamiltonian operator and other parameters are defined in Fig. 4.
is the molecular orbital coefficient of atom i contributing to the
The temperature-dependent factor F contains a summation over
ligand donor state and ri (L) is the distance from this atom to the
Franck–Condon factors, as well as the dependence of the energy
LnIII ion:
transfer on the energy gap; it is sometimes referred to as the energy 
mismatch factor. Assuming a Gaussian shape for the absorption and c2 · ri (L)
rDA = 
i i
(17)
emission bands, as well as wLn  wL , which is always true for c2
i i
f–f transitions, this factor can be expressed as:
 
The calculated transfer rates are in the range 107 –108 s−1 for
1 ln 2 E
2 3 T→Eu(5 D ) and ≈107 s−1 for 1 S→Eu(5 L6 ). In the initial model
1
F= exp − ln 2 (14) 4
WL  WL
4f |L in Eq. (15) was replaced by a squared distant-dependent
screening factor, (1 − 0 )2 , which led to overestimate these rates
Energy transfer mechanisms taken into account are: to 1010 –1011 s−1 for the former and ≈109 s−1 for the latter. How-
ever, the rates estimated for Dexter’s mechanism remain much
a. Exchange (Dexter) mechanism. After excitation of the ligand sin- faster than typical intra-configurational 4f–4f decay rates so that
glet state and intersystem crossing, the electron in the triplet conclusions reached in initial works are not altered [79].
state is transferred onto one of the excited LnIII states. Simul- b. Dipole–dipole (Förster) mechanism. After excitation of the ligand
taneously, an electron from the highest occupied 4f orbital is 1 S state and intersystem crossing to the donor 3 T state, the

transferred onto the ligand, filling up the gap created by the ini- excited electron returns to its initial orbital while transition
tial photoexcitation. The rate of transfer depends on the overlap dipole moments of the ligand and EuIII ion couple resulting in
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 27

excitation of the latter. The rate of energy transfer via this mecha-
nism depends on (i) the spectral overlap JDA defined above, (ii) the
luminescence quantum yield of the donor QD , (iii) the lifetime of
the donor excited state, (iv) the relative orientation of the donor
and acceptor transition dipoles , and (v) the distance between
the donor and the acceptor according to a rDA −6 dependence. The
corresponding equation reads as follows:
This mechanism is particularly effective if ˝2 is large and rDA
relatively short (<5–6 Å). The other two mechanisms need large
˝4 and ˝6 parameters to contribute substantially to the overall
transfer process.
Selection rules are embedded in the reduced matrix elements
which appear in Eqs. (15), (18) and (22):

4 e2 SL (1 − 1 )2    2 |J − J  | ≤  ≤ J + J  (J = J  = 0 excluded)
˝ ˛ J  U ()  ˛J
dd (24)
WET = F (18)
 (2J + 1) G · r 6
DA  for dipole–2 pole and dipole–dipole mechanisms and
where SL is the dipole strength associated with the ␸→␸ J = 0, ±1 (J = J  = 0 excluded) (25)
transition in the ligand, (1 − 1 )2 is the squared Sternheimer
shielding factor due to the filled 5s2 5p6 sub-shells, ˝ are JO for the exchange mechanism.
intensity parameters ( = 2, 4, 6), U() is a unit tensor opera- Finally, the kinetic model expresses the variation in the popu-
tor the reduced matrix elements of which are tabulated [52], lation of the levels implied under steady-state approximation (see
and (1 − 1 )2 is a distance-dependent squared screening factor right part of Fig. 4 for definitions):
[79]. ∂
i  
Experimentally, the efficiency of energy transfer is calculated =− kij
i + kji
j = 0 (26)
∂t
from the lifetimes in the presence,  obs , and in the absence,  0 , of j=1 j=1
transfer and can be related to the D–A distance and to the critical
j=
/ i j=
/ i
Förster distance R0 (corresponding to 50% transfer):
obs 1 The system of equations is solved by Runge–Kutta method and

et = 1 − = 6
(19) the theoretically estimated quantum yield is given by:
0 1 + (rDA /R0 )
Atot ·
j
R06 = 8.78 × 10−25 (2 · QD · n−4 · JD ) [cm−6 ] (20) Q = (27)
 ·
i

F(˜) · ε(˜) · ˜ −4 d˜
JD =  (21) here Atot refers to the sum of the radiative and non-radiative rates
F(˜)d˜ (=1/ obs ) and  is the pumping rate in photons/s.
The model involves quite a few approximations and requires
n is the refractive index and the isotropic limit to  is 2/3; F(˜) is
estimating several parameters, such as non-radiative decay rates
the luminescence spectrum recorded on an energy scale.
between LnIII excited levels (on the order of 106 s−1 ) or the
c. Dipole–multipole (2 ) mechanisms. These mechanisms are less
lifetime of the donor state(s) at the temperature at which the
known, but they can nevertheless contribute greatly to the
transfer occurs. Another point is that the ZINDO procedure largely
energy transfer process [64]. Their general expression is:
overestimates the energy of the singlet state when the excitation
2 e2 SL    2 window is chosen such as to reproduce closely the triplet-state
 ˛ J  U ()  ˛J
mp
WET = F (22)
 (2J + 1)G energy. Overall, however, the model yields reasonably good
 results, often within less than ±20% of the experimental value, as
With   being defined as: shown in Table 3. In fact sets of rate constants are often optimized
2
to reproduce the experimental quantum yield [71] so that the

r   2 predictive power of the model is still somewhat limited. On the
 = ( + 1)
||C () || (1 −  )2 (23)
(+2) 2 other hand, once adequate sets of rate constants are at hand, one
(rDA )
clearly sees by which main route the energy is transferred onto the
where
r   is the radial expectation value of r for 4f electrons metal ion. In most cases, the predominant path for EuIII complexes
( = 3), C() is a Racah tensor operator,  ’s are screening factors involves the triplet state of the ligand, transfer from the singlet
for the 5s2 5p6 subshells, and  = 2, 4, 6. Therefore the distance state being much less efficient. This is illustrated in Fig. 5 for the
dependence is (1/rDA )8 for the dipole–quadrupole mechanism. dimeric complex (NBu4 [Eu(L1)])2 (Scheme 1): transfer from 1 S is

Table 3
Selected data for EuIII complexes in the solid state at room temperature: experimental triplet (E0 –0 (3 T)) or LMCT (ELMCT ) state energies, calculated and experimental quantum
L
yields (QLn , %). Relevant chemical formulae are given in Scheme 1.

Compound E0 –0 (3 T) (ELMCT )/cm−1 L

Calc. QLn /% L
Exp. QLn /% Ref.

[Eu(tta)3 (TPPO)2 ] 20 661 73 73 [85]

[Eu(tta)2 (NO3 )(TPPO)2 ] 21 645 65 68 [85]
[Eu(btfa)3 (H2 O)2 ] 21 595 19 22 [86]
[Eu(btfa)3 (phen)] 21 633 50 38 [87]
[Eu(btfa)3 (phenNO)] 19 600 56 65 [86]
[Eu(btfa)3 (bpy)] n.a. 57.6 43 [87]
[Eu(btfa)3 (4,4 -bpy)(EtOH)] 20 276 46 37.8 [88]
d-U-[Eu(btfa)3 (4,4 -bpy)]a 21 473 52.5 51.0 [88,89]
(NBu4 [Eu(L1)])2 21 320 51 54 [76]
[Eu(L2)3 (H2 O)2 ] 20 200 (24 753) 24.3 20.5 [90]
[Eu(L3)3 (H2 O)2 ](H2 O)2 20 554 (24 474) 10.5 2.3 [90]
[Eu(nta)3 (t-DAB)] 19 650 (17 800) b
1.6 × 10−2 [91,92]
[Eu(L4)3 ](ClO4 )3 c 21 300 (<25 000) 6.7 × 10−5 2 × 10−3 [93,94]
a
In a di-ureasil host.
b
No quantitative determination but the quantum yield is reported to be very small [92].
c
1 mM solution in anhydrous acetonitrile.
28 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

R1 Ph
O
CF3 Hhfa
Ph P Ph
S
O N N
Htta O
TPPO Phen
F3C

Ph Hbtfa
R1 =
Hnta N N
N N
bpy
O
Hdbm PhenNO
N N
O

O O 4,4'-bpy
HO
Me
N O Me N C C N Me
O H H
3
HO t-DAB
O H2DP3C1
O O P
2 O 2
EtO
HO2C N CO2H DPPOT
H2dpa N N
HO N
F3C CF3
O N N

HO L4
O
O
O
R1
O O N
O N
O
OH
OH N R2
O HL5x
F 3C H4L1 CF3
OH H
H
O N N O

OH HO
OH
R = H HL2 O O
R Se R R
R = Cl HL3
O NHMe NHMe
H2L6x

Scheme 1. Chemical formulae of the ligands for complexes listed in Table 3 and Figs. 6 and 7.

40 negligible; moreover, in line with the above discussion, transfer

S from 3 T occurs almost equally onto 5 D1 (∼44%) and 5 D0 (∼56%)
[76]. Involvement of the 5 D1 state in the transfer process can be
30 detected experimentally by recording the time evolution of the
Energy /103 cm-1

5 D and 5 D luminescence: if 5 D contributes to the population of

1 0 1
5 D , its intensity should decrease with time and then the rise time
20 0
104 of 5 D0 should match the decay time of 5 D1 . Such determinations
are still scarce [80–82]. Indeed, detecting weak 5 D1 luminescence
10 is not easy, especially, when the EuIII ion is coordinated to carbonyl
groups or water molecules the vibrations of which (C O stretch or
S HOH bending) fairly well match the 5 D1 –5 D0 gap [83,84]. It is to
0
Ligand All rate constants in
be stressed here that evidencing 5 D1 luminescence is not a proof
that this level is populated through ligand energy transfer since
Fig. 5. Schematic energy level diagram, energy transfer processes and transfer rate it may be simply be populated by thermal excitation from 5 D0
constants for (NBu4 [Eu(L1)])2 . given the small energy difference between these two levels. Two
Reproduced with permission from Ref. [76], © 2014 American Chemical Society. convincing examples of 5 D1 populating 5 D0 have been recently
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 29

Fig. 6. Decay of the 5 D1 luminescence and building up of the 5 D0 emission in

Na3 [Eu(DP3C1)3 ] complex in the solid state at room temperature, exc = 320 nm.
Reproduced with permission from Ref. [82], © 2013 The Royal Society of Chemistry.

published featuring [Eu(NO3 )3 (DPPOT)3 ] [81] (see Section 2.5)

and a tris(dipicolinate) complex in which a coumarin sensitizer is 0.8
coupled to the 4-position of the pyridine ring, Na3 [Eu(DP3C1)3 ] Q LEu
(see Scheme 1): in the latter, the decay of the 5 D1 luminescence
0.7
intensity perfectly matches the growing up of emission from 5 D0
as shown in Fig. 6; both decay and rise times are around 1.3 ␮s [82].
Data listed in Table 3 reveal interesting features. Firstly, they
0.6
point to the detrimental quenching of water molecules bound
0.5 5D 5D
in the inner coordination sphere. Secondly, when examining the 1 2
series of chelates with btfa− it becomes evident that the nature
of the ancillary ligand, as well as the matrix into which the 0.4
complex is embedded, is critical and can be used to tune the photo-
physical properties. Thirdly, when comparing [Eu(L2)3 (H2 O)2 ] 0.3
with [Eu(L3)3 (H2 O)2 ](H2 O)2 , for instance, one realizes that water 1.5 2.0 2.5 3.0 3.5 4.0 4.5
molecules bound in the second coordination sphere have also
E0-0(3T)-E(5D0) / 103 cm-1
a large quenching effect since the quantum yield predicted for
[Eu(L3)3 (H2 O)2 ](H2 O)2 is far larger than the experimental one. The
last four entries feature complexes in which charge-transfer states 0.4 Q LTb
have been identified; they will be discussed in Section 2.5.
Improving such model calculations may come from the consid- 0.3 5D
eration of ligand relaxation in the excited state which occurs on 4
the time scale of a vibration that is several orders of magnitude 0.2
faster than the energy transfer processes. High-level calculations
(state-specific and state-averaged CASSCF, allied with extended 0.1 b
multi configurations) taking this fact into consideration recently
succeeded in explaining why energy transfer in [Eu(tta)3 (phen)] is 0.0 a
more efficient than in [Eu(tta)3 (bpy)] [95].
19 20 21 22 23 24 25
2.3. Role of triplet states E0-0(3T) / 103 cm-1

Triplet states play a central role in energy migration between
organic ligands and LnIII ions, and vice versa, by either participat-
ing in the sensitization process, when the lowest energy triplet
state, with 0-phonon energy, E0–0 (3 T), is located above the emit-
ting state, or by quenching the metal-centred excited state when
it lies below it. The few systematic works published so far have
focused on the relationship between E0–0 (3 T) and the quantum
yield of visible-emitting EuIII and TbIII chelates. Their main findings
are summarized below.
In an early, seminal, study published in 1970, S. Sato and M.
Wada reported the quantum yields and lifetimes of EuIII and TbIII
tris and tetrakis(␤-diketonates) [80], along with time-resolved
experiments to demonstrate the mechanism of energy transfer and
the role of the 5 D1 level. They showed that the quantum yield
reaches a maximum when E0–0 (3 T) is about 1200 cm−1 above the
5 D level (or 3750 cm−1 above the 5 D level, see Fig. 7, top). The
1 0
largest quantum yield is obtained for [Eu(tta)4 ]− : 55% in acetoni-
trile at room temperature, E0–0 (3 T) = 20 300 cm−1 . Time-resolved
spectra for chelates for which E0–0 (3 T) > E(5 D1 ) clearly show 5 D1
emission dominating the luminescence spectrum during the first
Fig. 7. (Top) Quantum yields of EuIII tetrakis(␤-diketonates) in acetonitrile versus
triplet-state energy [80]. (Middle) Quantum yields of solid state samples of
[Eu(L5x)3 ] complexes versus the 3 T–5 D0 energy difference; black squares: alkyl sub-
stituents; red circles: aryl substituents [96–98]. (Bottom) Quantum yields of TbIII
chelates [Tb(L6x)2 ]− in 0.1 M Tris buffer containing 0.2% DMSO versus energy of the
triplet state.
Redrawn from Ref. [99].
microsecond after the excitation pulse and then disappearing to
the benefit of 5 D0 emission, in line with the latter level being pop-
ulated by 5 D1 . When the triplet state lies between 5 D1 and 5 D0 ,
direct transfer to the latter occurs, but if 3 T is almost resonant with
5 D , back transfer considerably reduces the quantum yield. Finally,
0
when E0–0 (3 T) < E(5 D0 ), no sensitization occurs. For TbIII chelates,
the optimum energy gap 3 T–5 D4 is about 2400 cm−1 , which is low-
ered to 800 cm−1 when the temperature is decreased to 100 K.
Although much less detailed in terms of analysis of the energy
transfer mechanisms, a study of 41 luminescent EuIII and TbIII
aminocarboxylates in water by M. Latva et al. [100] is often
cited. For EuIII , the situation is complex because both 5 D1 and
5 D can play the role of receiving states and, moreover, data
2
30 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
display a large spread. QEu L values tend to increase when 3 T is
above 5 D1 , in line with energy transfer on the Eu(5 D1 ) level and
coherent with selection rules for Dexter mechanism. With increas-
ing E0–0 (3 T) energy, the quantum yield then slightly decreases
followed by another increase when the triplet state becomes res-
onant with the 5 D2 level; in summary, favourable situations are
when the E0–0 (3 T) − E(5 D0 ) gap is in the ranges 2500–2800 cm−1 or
4000–6000 cm−1 . For TbIII chelates, quantum yields are the largest
when the energy difference between the triplet state and the emis-
sive Tb(5 D4 ) level is around 2000 cm−1 . Authors are using these
results as phenomenological rules of thumb for tailoring the coor-
dination environment of luminescent compounds. However, one
has to realize that the quantum yields reported for EuIII chelates
are mostly smaller than 25% (with one exception at 38%), pointing
to quenching by diffusing water molecules. In addition, consider-
ing only one parameter is an oversimplification given that several
levels may be simultaneously involved in the transfer process. The
influence of charge transfer states and of potential hydration of the
complexes is also neglected in this approach.
Another investigation deals with a series of 16 solid-state
samples of 9-coordinate EuIII complexes with benzimidazole-
substituted pyridine-2-carboxylates, [Eu(L5x)3 ] (Scheme 1) that
have their coordination sphere saturated and display quantum
yields up to 70% [97,98]. The benzimidazole moiety has been dec-
orated in R1 with alkyl or aryl groups, and in R2 with F, Cl, Br, Me,
or OR substituents. The correlation with the triplet state energy in
the range 18 800–21 300 cm−1 is relatively smooth, at least for lig-
ands bearing alkyl substituents in R1 (Fig. 7, middle) and shows that
quantum yields are sizeable when the 3 T–5 D0 energy difference is
in the range 2000–4000 cm−1 in line with the conclusions reached
for ␤-diketonates and polyaminocarboxylates.
Finally, an investigation of the antenna effect for TbIII
chelates has been conducted with para-substituted 2-
hydroxyisophthalamide ligands H2 L6x [99]. Energies of ligand
absorption and fluorescence maxima as well as of the lowest
triplet state are in linear correlation with the Hammett parame-
ters, increasing with the ␲-withdrawing ability. Time-dependent
density functional theory (TD-DFT) calculations also show that the
singlet-triplet gap decreases with increasing Hammett parameters,
favouring intersystem crossing. Data for the quantum yields are
displayed in Fig. 7 (bottom) and feature S-shape behaviour, with a
sharp increase in QTb L values when E 3 −1 above
0–0 ( T) is >1200 cm
the emitting 5 D4 level. Two complexes, however, are out of the
correlation; their ligands bear NO2 (a) and Br (b) substituents.
For the former complex the reason is clear in that the TD-DFT
calculations point to the presence an ILCT state probably lying
lower than the 3 T state and quenching luminescence. As for the
brominated ligand that has E0–0 (3 T) only 180 cm−1 lower than the
chlorinated one (QTb L = 0.30), no definite explanation has been put
forward by the authors who suspect a heavy atom effect.
In conclusion for both EuIII and TbIII chelates, if the ligand triplet
state is the main donor state, it should lie at least 1500 cm−1 above
the emitting level to avoid too much back transfer and the ideal
energy gap lies between 2000 and 4000 cm−1 . This is however a
mere guideline and not a rule, since the presence of charge-transfer
states (ILCT, LMCT) can substantially change this picture.
There are no such systematic studies for the other LnIII ions.
Some of them have much more complex electronic structures so
that extrapolation of the above rules of thumb should be made with
care.
2.4. Role of singlet states
The role of singlet states in ligand-to-metal energy transfer
is largely ignored for three main reasons. The first one lies in
Scheme 2. Chemical formulae of ligands for the complexes described in Section 2.4.
the successful interpretation of energy transfer in many EuIII and
TbIII chelates with a singlet-triplet-LnIII path, as ascertained by
the wealth of publications dealing with the design of lumines-
cent LnIII compounds with organic ligands based on this concept.
Secondly, since singlet states have very short lifetimes, their impli-
cation in the transfer process is not simple to demonstrate, unless
fast spectroscopic equipment is at hand. Finally, singlet-state trans-
fer is often only partial [81] and its contribution to the overall
transfer difficult to decipher. Theoretical modelling (see Section
2.2) however shows that these states can participate in the trans-
fer, especially that there are often several of them with suitable
energies for transfer on higher lanthanide excited states that are
quite numerous. There are only a few examples for which sin-
glet state transfer has been specifically taken into consideration
in the overall energy transfer path because usually only indirect
proof can be found. For instance, modelling of the energy transfer
between tryptophan moieties of calcium-binding proteins and TbIII
ions explicitly involved the spectral overlap between tryptophan
fluorescence band and metal-ion absorption spectra [101].
Detailed and quantitative spectroscopic studies dealing with
the involvement of 1 S states in the energy-transfer process by
lifetime measurements and/or triplet-triplet (3 T–3 T) transient
absorption spectroscopy (TAS) and related time-resolved evo-
lution are still scarce. In one recent example, no triplet state
involvement has been postulated in the sensitization of EuIII lumi-
nescence in Na3 [Eu(DP3C1)3 ] (Scheme 1) because time evolution
of 3 T–3 T TAS for both EuIII and GdIII complexes is the same at
room temperature with a lifetime of 2.9 ± 0.5 ␮s and, moreover,
EuIII emission from 5 D1 starts a few ns after the initial excita-
tion pulse [82]. A more complex system consisting in an EuIII
complex with a DOTA-appended 1,8-napthalimide ligand H3 L8
(Scheme 2) and its GdIII counterpart, has been investigated both
in water and in acetonitrile. Aggregation takes part so that spec-
tra are concentration-dependent, which makes interpretation quite
involved. Nevertheless, from TAS and lifetime data, the authors
concluded that both singlet and triplet state sensitization was oper-
ative, the former with a much larger rate constant (∼109 s−1 ) than
the latter (∼104 s−1 ). This came to a surprise since usually 3 T trans-
fer is much faster than 1 S transfer. In this system, however, the
1 S–EuIII transfer rate occurs on a time scale similar to the intersys-
tem crossing and, moreover, the overlap between EuIII absorption
and triplet emission is much smaller compared with singlet emis-
sion [102].
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
26
24 singlet
1LMCT
isc
22
E / 103 cm-1
20
18 triplets
L7 tta
Fig. 8. (Left) Proposed ligand–EuIII energy migration paths through singlet (red lines) [103], triplet (yellow lines) [104], or 1 LMCT (blue lines) [66] states in [Eu(tta)3 (L7)].
(Right) Formula of the ancillary ligand L7.
That positive identification of a singlet-state-mediated trans-
fer is difficult is exemplified by the investigation of a bright
yellow ␤-diketonate ternary complex with dipyrazolyl-triazine,
[Eu(tta)3 (L7)] (see Fig. 8) in toluene [103]. The ancillary ligand pos-
sesses a 1 S state located at 24 600 cm−1 in the complex and which
has 1 ILCT character. Room-temperature time-resolved lumines-
cence spectra after excitation into this level display initial emission
from the ligand singlet state with lifetime in the range 1.3–1.8 ns;
Eu(5 D1 ) emission is also seen with a rise time of 1.8 ns and a decay
time of 0.39 ␮s. Both signals then disappear to the benefit of the
5 D emission which grows with a rise time of 0.39 ␮s and a decay
0
time of 0.48 ms. At low temperature (77 K), ligand phosphorescence
is detected with E0–0 = 20 800 cm−1 and lifetime of 3.9 s, while 5 D0
emission has a decay time of 0.65 ms. Considering these facts and
the large decrease in ligand emission quantum yield from 75% for
the free ligand to 1% in the EuIII complex, the authors concluded that
sensitization of EuIII luminescence is essentially achieved through
the singlet state (Fig. 8, red arrow). This conclusion has been chal-
lenged soon after and data rationalized in an alternative way as
follows (yellow mechanism in Fig. 8) [104]. The triplet state of
tta (E0–0 ≈ 21 000 cm−1 ), which is known to sensitize efficiently
EuIII luminescence by transfer to both 5 D1 (5 D1 ←7 F0,1 ) and 5 D0
(5 D0 ←7 F1 ) levels through the exchange mechanism (J = 0,±1) is
almost resonant with the triplet state of L7 (20 800 cm−1 ). Therefore
the energy migration path 1 ILCT(L7)–3 T(L7)–3 T(tta)–Eu(5 D1 ,5 D0 )
becomes feasible: the transfer from 3 T(tta) to Eu(5 D1 ,5 D0 ) is fast but
3 T(tta) is populated by the slow decaying 3 T(L7) state and therefore
the apparent lifetime of 3 T(tta) is lengthened accordingly, which
explains why 5 D0 luminescence still occurs 1 s after the excita-
tion pulse, indicating that the EuIII emissive level continues to be
populated in this time frame by the triplet states. The second inter-
pretation points to the importance of considering the rates at which
energy migrates between states and not only the energy of the
implied levels! The [Eu(tta)3 (L7)] complex was subsequently re-
investigated by ultrafast spectroscopic techniques, giving attention
to the initial fast quenching of the ligand excited singlet state [66].
The study revealed that ligand fluorescence occurs in two distinct
phases with decay times 8.5 ps and 1.8 ns. A third mechanism was
therefore invoked postulating the presence of a spectroscopically
silent singlet state with charge transfer character, 1 LMCT (blue path
on Fig. 8). The shorter decay time of the ligand fluorescence thus
corresponds to a 1 S(L7)→1 LMCT(L7,Eu) fast transfer with estimated
98% efficiency. The longer lifetime is assigned to delayed fluores-
cence due to thermally activated 1 LMCT(L7,Eu)→1 S(L7), by back
31
N
5D
2
5D
1 N N
5D
0 N N N
N N
EuIII L7
transfer, an explanation substantiated by temperature-dependent
measurements. Thus the 1.8 ns lifetime corresponds to the lifetime
of the 1 LMCT state which feeds the 5 D1 level.
Other evidences for singlet-state excitation of lanthanide ions
are non-observation of the triplet state (e.g. absence of ligand phos-
phorescence for the GdIII complex) [105] or localization of the
triplet state below the emitting state, especially for TbIII chelates,
as exemplified for dinuclear macrocyclic Schiff base complexes
[106,107], a TbIII ZnII heterometallic cryptate [108], or the TbIII
complex with 2-mercaptobenzothiazole [109].
Sensitization of the luminescence of NIR-emitting LnIII ions
is more prone to involve energy transfer from 1 S states, partic-
ularly for the ions having several excited electronic levels above
30 000 cm−1 . For instance, energy transfer in polylysine dendrimers
bound to NdIII and ErIII ions has been assigned to the fluorescent 1 S
state of the built-in dansyl chromophores [110]. However, the 3 T
route is not excluded and can be operative in parallel. Important
parameters to be considered in addition to the spectral overlap are
the rate of the intersystem crossing process and selection rules for
energy transfer. The behaviour of dansyl and lissamine substituents
that sensitize NdIII luminescence in a tris(carboxylate) complex
with derivatized ligands fitted with these dyes, but not ErIII and
YbIII emission, can be rationalized taking these parameters into
account [111]. Complexes with derivatized boron dipyrromethene
(Bodipy) ligands, [Ln(L9)3 ] (Ln = Er, Yb), are also sensitized via
Bodipy singlet state: no triplet state phosphorescence is observed,
even for the GdIII complexes and the lowest 1 S fluorescence
band overlaps the Er(4 F9/2 ←4 I15/2 ) absorption band while the
1 S-Yb(2 F −1 [112].
5/2 ) energy gap amounts to only 5700 cm
2.5. Role of charge-transfer states and photo-induced electron
transfers
Several types of charge transfer states may be implied in sensi-
tizing or quenching LnIII -centred luminescence: (i) ligand-centred
charge-transfer states such as ILCTs which are usually singlets, as
well as singlet and triplet MLCT states present in transition metal
containing chromophores, and (ii) LMCTs and MLCTs between the
ligand(s) and the lanthanide ion.
2.5.1. Intraligand charge transfer states
In fact, ILCTs have not always been identified because they
sometimes are simply the lowest singlet excited state and a the-
oretical approach is needed to determine the composition of the
32 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
Scheme 3. Ligands generating ILCT and LMCT states documented in Section 2.5.
corresponding wavefunctions in order to positively identify an ILCT
contribution. Optical transitions of ILCTs also often overlap with
the lowest *␲←␲ absorption band. To the best of our knowledge
the role of ILCT states has been specifically pointed out for the
first time by V.F. Zolin and collaborators who studied EuIII and
TbIII pyridine-carboxylates [113]. Similar states have subsequently
been identified in several classes of compounds, such as dansyl-N-
methylaminobenzoates [114], 2:1 complexes with calix[8]arenes
[115], carbazole-functionalized ␤-diketonates [116], aromatic ␤-
diketonates bearing amine groups [117], EuIII chloride adducts with
phenanthroline [118] and 2,2 -bipyridine [65], complexes with
benzoxazole-substituted 8-hydroxyquinolines [57], 4-benzyloxy
benzoates [119], substituted [2.2]paracyclophanes [120], or
tetrathiafulvalene-amido-2-pyridine-N-oxide [121] for example.
The role of the ILCT state varies depending on the nature of the
LnIII ion and of other bound ligands, as well as on its energy.
It may function as the main energy donor state, selected exam-
ples being [Ln(L10)3 (tpy)] (Ln = Nd, Er) [114], L11[Eu(tta)4 ] [122],
Na[Yb(L12x)4 ] [57], [Yb(hfa)3 (L13)2 ] [121], [Eu(L14)3 (bpy) [120]],
or [Er(hfa)3 (L15)] [123], see Scheme 3 for ligand structures. The
ILCT states are usually located at low energy, so that excitation of
the LnIII ions can be achieved in the visible, a definite advantage
for several applications. In addition, the dipolar nature of ligands
generating ILCTs makes them amenable to multiphoton excitation,
another benefit, particularly when it comes to luminescent bio-
probes [124]. Sometimes, ILCT states simply act as relays between
the singlet and the triplet states, as demonstrated for adducts of
europium chloride with phenanthroline and bipyridine [65,118],
or between singlet and LMCT states [117]. When the energy of the
ILCT state is too close to the emitting level or to a donor ligand
level, it has a quenching effect, see for instance [Tb(L16)3 (solv)n ]
(solv = DMSO, H2 O) [119].
2.5.2. Ligand-to-metal charge-transfer states
Luminescence sensitization of EuIII and, to a lesser extent
SmIII , TmIII , and YbIII , by LMCT states has been investigated in
details, especially for inorganic compounds since these states lie
far above the emitting states and are commonly used to excite
luminescent ions in lamp and display phosphors. When it comes
to complexes with organic ligands, LMCT states play equivocal
role in that their energies can be considerably lowered by covalent
contributions to the bonding, down to 27 800 cm−1 in aromatic
ct | = 0.01, 0.05, and 0.1. The effect of the LMCT state is
carboxylate and nitrato complexes with sulfoxides [125], or even
to 20–22 000 cm−1 in some other complexes [48,66]. For EuIII
for instance, strong quenching of luminescence usually occurs if
E(LMCT) < 22–24 000 cm−1 , whereas positive contribution to the
sensitization of the LnIII ion luminescence occurs when the LMCT
state has higher energy [66]. In fact, the influence of an LMCT
state on the quantum yield depends on its energy with respect
to both ligand and metal-ion levels and on the importance of the
crossing over between this state and the excited and ground term
manifolds of the LnIII ion, i.e. in the case of EuIII , the 5 D and/or 7 F
spectroscopic terms.
A theoretical approach has been worked out for EuIII consid-
ering two-electron Coulomb and exchange interactions and from
which selection rules may be derived, transfer rates estimated, and
quantum yield calculated [92,126]. The model taken into consider-
ation is represented on the left hand side of Fig. 9. Energies of the
triplet and singlet states have been set at 20 000 and 30 000 cm−1 ,
respectively. Decay rates were chosen as follows: 108 s−1 for S1 →T
intersystem crossing and for LMCT→S0 transfer; 106 s−1 for T→S0
intersystem crossing, S1 →S0 internal conversion, and nonradiative
decay rates in the EuIII ion, with the exception of 5 D0 →7 FJ for which
103 s−1 was selected; the total radiative rate of 5 D0 was also set to
103 s−1 . The transfer rates involving ligand and LMCT states were
estimated according to the procedure outlined in Section 2.2 tak-
ing into consideration both the J mixing between 7 F0 and 7 F2 (on
the order of 5%) and the 7 F1 population at room temperature (30%).
Three different situations have been modelled.
(i) In addition to ligand-to-EuIII energy transfer, another
transfer occurs between the metal ion and the LMCT
state. In this scheme, luminescence is strongly quenched
when 5000 < E(LMCT) < 20 000 cm−1 , the charge transfer state
pumping out the population of 5 D1 and 5 D0 ; on the other hand,
if the LMCT state lies above 5 D4 (>27 600 cm−1 ) the quantum
yield behave as in a complex without LMCT state. It is note-
worthy that in the high energy range, the best quantum yield is
obtained when the LMCT state lies between 5 D1 and 5 D2 point-
ing to the importance of 5 D1 in the energy transfer process.
(ii) In addition to ligand-to-EuIII energy transfer, another transfer
occurs between the LMCT state and the ligand states. Three
values of the overlap integral between the wavefunctions of
the charge transfer state and of the ␲ states have been tested,
proportional to this integral. Two quenching domains are
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 33

There is, however, at least one pertinent case, the tris complexes
with 2-mercaptobenzothiazole, [Ln(L17)3 ] (Ln = Sm, Eu, Tb, Tm, see
Scheme 3) two of them only displaying luminescence, EuIII (triplet
state energy transfer) and TbIII (singlet state energy transfer) [109].
The 3 T state lies at 18 200 cm−1 and estimates of LMCT state ener-
gies for SmIII and EuIII by non-empirical density functional theory
yields 12 000 and 7000 cm−1 , respectively [127]. The SmIII (LMCT)
energy is therefore in the middle of the quenching range, explaining
the absence of luminescence for this ion while emission of EuIII is lit-
tle affected, the EuIII (LMCT) energy lying in the middle of the sharp
increase in quantum yield with increasing E(LMCT). Explanation for
the difference in luminescent properties between TbIII and TmIII is
different and pertains to a larger distortion of the triplet state with
respect to the fundamental singlet state in the TmIII complex: in
the presence of such a distortion, the zeroth vibrational level of the
excited triplet state is located below the intersection of the sin-
gle configurational curve of this state with the 4f manifold, so that
energy transfer will be operative only as long as higher vibrational
states are populated [127].
Going back to the last four entries of Table 3, the LMCT state
in [Eu(L2)3 (H2 O)2 ] and [Eu(L3)3 (H2 O)2 ](H2 O)2 (E > 24 500 cm−1 )
does not have a quenching effect: the low values of QLn L can be

explained entirely by the presence of the inner- and outer-sphere

water molecules. On the contrary, [Eu(nta)3 (t-DAB)] is indeed
non-luminescent, as predicted, because the LMCT is located at
17 800 cm−1 , just above the emissive Eu(5 D0 ) level and can eas-
ily deactivate both the 5 D0 (17 300 cm−1 ) and 5 D1 (19 000 cm−1 )
levels [91]. Only weak luminescence has been reported for
[Eu(L4)3 ](ClO4 )3 , E(LMCT) < 25 000 cm−1 . Modelling for this com-
pound reproduces the experimental situation when a LMCT state
with energy close to 1 S is introduced. It is noteworthy that when the
LMCT state is shifted to higher energy in [Eu(NO3 )3 (L4)(MeOH)], a
reasonable value for QLn L is restored [93]. The presence of CT state

at around 22 800 cm −1 has also been invoked for explaining the

weak luminescence exhibited by the dimeric complex [Eu2 (L18)6 ]
(Scheme 3) [128].

2.5.3. Metal-to-ligand charge-transfer states

For most of the LnIII ion, these states lie at very high energy,
Fig. 9. Effect of LMCT on the quantum yield of EuIII : (Top) energy diagram used in typically >50 000 cm−1 , with the exception of CeIII (see Section
the model (redrawn after Ref. [92]). (Right) quantum yield versus LMCT energy for 3 1.2) and some inorganic TbIII materials [129], so that they do not
values of the overlap integral between CT and ␲ wavefunctions
ct | = 0.01 (full
play a role in either energy transfer processes or emission spectra.
line), 0.05 (dashed line), and 0.10 (dotted line).
Nevertheless, there are several literature entries wrongly invoking
Reproduced with permission from Ref. [92] © American Institute of Physics 2005.
MLCT (and without experimental proof of their existence) in energy
transfer schemes, particularly for EuIII and TbIII complexes.
observed, which are associated with the exhaustion of the
populations of the S1 and T1 levels, respectively. Minima in
2.5.4. Relationship with redox properties (photoinduced electron
the quantum yield occur when E(LMCT) is about 1500 cm−1
transfers)
smaller than E(S1 ) or E(T1 ).
The quenching effect of LMCT states described above consid-
(iii) The third case combines the previous two ones, taking into
ers these states simply as additional electronic levels implied in
account forward and backward transfers involving (i) the
the overall energy migration process. However depending on ther-
LMCT state and the ligand 1 S and 3 T states, (ii) the LMCT state
modynamic conditions, the presence of a LMCT state may lead to
and the LnIII excited states, and (iii) the ligand 1 S and 3 T states
reduce the *LnIII centre into *LnII , resulting in the disappearance
and the LnIII excited states. The variation of the quantum
of the f–f transitions. The process is called photoinduced elec-
yield with E(LMCT) is depicted on the right part of Fig. 9.
tron transfer (PET) and occurs when the electrochemical reduction
There are two quenching domains, the first one corresponding
potential of the ligand excited state Er (L•+ /L*) is more negative than
to E(LMCT) in the range 5000–20 000 cm−1 and leading to
the reduction potential of LnIII ; it has largely been documented for
almost complete obliteration of the luminescence. Evalua-
EuIII (−0.35 V vs SCE). The driving force of the process, GPET , can
tion of the energy transfer rates shows the ligand-to-LMCT
be estimated as follows:
rates being higher by at least two orders of magnitude than •+
EuIII -to-LMCT transfer rates. The second quenching range GPET = −Er (L /L∗ ) − E(L∗ ) − Er (EuIII /EuII ) (28)
corresponds to LMCT energies becoming close to the energy
where E(L*) is the energy of the excited singlet or triplet state trans-
of the excited singlet state. Such a case has been documented
ferring the electron.
for [Eu(L4)3 ](ClO4 )3 (Scheme 1) [93].
Such a mechanism is operating in the europium complex with
The low-energy domain for which quantum yields are insen- diphenylphosphanoethane, [Eu(NO3 )3 (DPPOT)3 ] (Scheme 2) which
sitive to the LMCT state is difficult to explore experimentally. is thermodynamically stable in MeCN/CHCl3 , with log ˇ13 = 20.8
34 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
Table 4
Photophysical parameters for DPPOT and [Eu(NO3 )3 (DPPOT)3 ] in CHCl3 /MeCN (20/80, v/v) at room temperature [81].
Parameter DPPOT Eu(DPPOT)3
QF /% 20 2.5
 S /nsa 0.31 0.088
 T /␮s 4.5 ± 0.5 0.5 ± 0.1
ISC /% n.a. 7 n.a.
a
Average lifetime (3-exponential decay).
[81]. Steady-state and time-resolved measurements in nanosec-
ond, microsecond, and millisecond time frames of both ligand
and europium luminescence yield the photophysical parameters
reported in Table 4 and the following overall picture of the various
energy migration paths operative in this complex is sketched on
Fig. 10.
Both the fluorescence quantum yield and lifetime of the ligand
singlet state are considerably reduced in the complexes. In par-
allel, luminescence from the Eu(5 D1 ) level is recorded with a rise
time of 0.5 ␮s exactly corresponding to the lifetime of the triplet
state in the complex, confirming the transfer onto 5 D1 . Moreover,
analysis of time-resolved fluorescence shows that energy is also
transferred from 1 S, in the proportion of 20%, the remaining 80%
being transferred from 3 T. With time, Eu(5 D1 ) luminescence fades
of to the benefit of Eu(5 D0 ) emission which occurs with a rise time
of 10 ± 1 ␮s, in reasonable correlation with the Eu(5 D1 ) decay time
(15 ␮s), pointing to population of the emissive 5 D0 level by 5 D1 .
Despite the long lifetime of Eu(5 D0 ), 3.08 ms, indicating a good
protection against nonradiative deactivation in the coordination
sphere, and the ideal location of the triplet state (21 000 cm−1 )
above the Eu(5 D1 ) state (19 000 cm−1 ), the quantum yield of the
EuIII complex is poor, 1%, reflecting the presence of a very effi-
cient quenching process. The electrochemical potential of DPPOT
is −2 V versus SCE and application of Eq. (28) gives estimated ther-
modynamic driving forces of −1.52 and −0.25 eV for the singlet and
triplet excited states, respectively. Deactivation of the ligand singlet
state through the PET process seems therefore thermodynamically
quite feasible and is mostly responsible for the poor quantum yield
of the Eu(5 D0 ) emission.
Photoinduced electron transfers are useful in the design of lumi-
nescent analytical probes and sensors [130]. In particular, LnIII
luminescence can be switched off or on depending on the absence
or presence of PET involving either the chromophoric ligand or the
metal ion.
Fig. 10. Energy migration paths in [Eu(NO3 )3 (DPPOT)3 ].
Redrawn after Ref. [81].
Tb(DPPOT)3 Parameter Eu(DPPOT)3
4.5 ± 0.5  (5 D1 )rise /␮s 0.5 ± 0.1
n.a.  (5 D1 )decay /␮s 15 ± 2
1.7 ± 0.2  (5 D0 )rise /␮s 10 ± 1
 (5 D0 )decay /ms 3.08 ± 0.03
In the first case, an electron-rich moiety functioning as electron
donor transfers one electron into the HOMO of the antenna when
it is linked to an analyte (Fig. 11, bottom), preventing energy trans-
fer on the LnIII ion. In the absence of interaction, the transfer does
not occur and luminescence sensitization can proceed (Fig. 11, top).
There are numerous examples of this case in bioanalyses; the PET
switch is typically a benzene derivative which sees its properties
altered by interaction with a biochemical molecule, e.g. a protease
such as microsomal leucine aminopeptidase. In the reported analy-
sis, the quantum yield of the EuIII and TbIII luminescence decreases
from 6.8 and 4.8%, respectively to 0.01, leading to highly specific
and sensitive time-resolved assays.
Similar turn-off probes have been proposed for various analyses:
(i) Detection of N-acetyltransferase (NAT) activity in recombinant
enzymes or cell lysates; the PET process is suppressed by inter-
action with NAT which catalyses N-acetylation of the aniline
moiety of the chromophore, suppressing the PET process. As a
result, TbIII luminescence is switched on [132].
(ii) Numerous reports deal with LnIII complexes with terpyridine,
which have been rendered responsive by adding PET function-
ality. These complexes are interesting because the triplet state
of terpyridine (∼22 200 cm−1 ) is able to sensitize both EuIII
and TbIII luminescence and the tpy excited state can be eas-
ily quenched by electron-rich substituents. A few examples are
described here. For instance, a EuIII probe for the detection of
nitric oxide in living plants and tissues is based on an o-diamine
switch reacting with NO to form benzotriazole in the presence
of oxygen [133]. Reactive oxygen species (ROS) such as • OH and
ClO− are detected with both EuIII and TbIII luminescence thanks
to a p-aminophenoxy substituent which is hydrolysed upon
reaction with these species [134]. Another system involves
ratiometric TbIII /EuIII analysis of intracellular biothiols with a
2,4-dinitrobenzene-sulfonyl switch onto which the tpy moiety
transfers an electron [135]. On the other hand, the probe spe-
cific for singlet oxygen and using an anthracene chromophore
which gets oxidized upon reaction with this species does not
work thanks to a PET mechanism, but rather, the anthracene
triplet state acts a sink preventing tpy to transfer energy onto
the metal ion [136].
Fig. 11. Control of LnIII luminescence by a PET switch acting on the chromophoric
antenna; the yellow circle symbolizes interaction with the analyte.
Redrawn after Ref. [131].
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 35

ksep F• +⋅⋅⋅Ln2+ 3. Minimizing radiationless vibrational de-activation

kdif kPET processes
F* + Ln3+ {1F*/Ln3+} {F• +/Ln2+}
k-dif ΔGPET
kbt F + Ln3+ In the 1960s it was recognized that dissolving LnIII salts in D2 O
rather than in water results in much brighter emission for EuIII
Scheme 4. Quenching mechanisms of aromatic hydrocarbons by LnIII ions (Ln = Eu,
Yb); F denotes the fluorescent hydrocarbon [137].
and TbIII but not for GdIII [139] and that the effect depends on the
energy gap between the emitting and receiving levels. Careful study
of the phenomenon in water, acetonitrile, and associated deuter-
ated counterparts led to two important conclusions: (i) quenching
[Ln(hfa)3(1An*-PB)] of the luminescence is due to high-energy vibrations (namely OH
CF3
N stretch for water) and (ii) coordinated water molecules act inde-
O
pendently [140]. Quenching is achieved through several phonons
Ln [Ln(hfa)3(An•+-PB•-)]
from different bound molecules and/or through overtones of the
O
N N implied vibration and therefore this multiphonon de-activation is
CF3
3 [Ln(hfa)3(3An*-PB)] temperature-dependent. Moreover, the radiationless deactivation
rate constant is highly sensitive to the LnIII -ligand distance. The
nature of the interaction is essentially dipolar-dipolar so that it can
[Ln(hfa)3(L19)] [Ln*(hfa)3(An-PB)]
be modelled with Förster’s mechanism [141]. In fact, minimizing
Scheme 5. (Left) Chemical formula for [Ln(hfa)3 (L19)], Ln = Nd, Gd, Er, Yb. (Right) radiationless deactivation is equivalent to maximizing the intrinsic
quantum yield QLn Ln .
proposed mechanism for sensitizing LnIII NIR luminescence; An denotes anthracene
and PB pyridylbenzimidazole units [138].

3.1. Quenching by OH vibrations and hydration number

The higher the vibrational overtone needed to bridge the energy

Regarding the second case, an example of a PET process involv-
ing LnIII ions is the quenching of aromatic hydrocarbons by EuIII and
YbIII ions. Two mechanisms are involved with switching between
them when GPET lies in the range −1.4 and −1.6 eV. When
GPET < −1.6 eV, the quenching effect of the LnIII ion occurs through
long-distance electron transfer and yields a geminate radical ion
pair (Scheme 4); the effective quenching distances are 5.0 and 8.0 Å
for YbIII and EuIII , respectively. When GPET > −1.4 eV, quenching
occurs by exciplex formation [137].
Finally, photoinduced electron transfer may play a role in
the sensitization of NIR LnIII luminescence as demonstrated for
tris(␤-diketonate) adducts with the chelating ancillary ligand L19
(Scheme 5). The anthracene moiety acts as a sensitizer for the
luminescence of NdIII , ErIII , and YbIII , according to a complex mech-
anism. Quenching of the ligand fluorescence occurs in parallel but
is also seen for complexes with non-luminescent ions, GdIII or ZnII .
This suggests that binding of a metal ion to the pyridylbenzim-
idazole unit strongly increases the electron attraction capability
of this moiety by stabilizing its LUMO. Intraligand photoinduced
electron transfer consequently takes place from the 1 S state of the
anthracene moiety to the coordinated diimine of the pyridylbenz-
imidazole group. Rapid back electron transfer follows, generating
the anthracene 3 T state which subsequently acts as energy donor
for the emitting LnIII ions, as demonstrated by transient absorption
measurements [138].
difference between the emitting level and the highest sub-level
of the receiving multiplet, Eg , the less likely is the quenching
phenomenon to occur. Relationship between the luminescence life-
times, Eg , and the number of phonons needed to bridge the energy
gap is illustrated in Table 5 in which ˜ (O H) = 3600 cm−1 and ˜
(O D) = 2200 cm−1 . The resulting correlation is commonly referred
to as the “energy-gap law” and is widely used when explaining
differences in quantum yields between LnIII ions in series of iso-
morphous compounds (see Fig. 3 for a rule of thumb).
Quantitative estimates of the contribution of different groups
(O H, C H3 , C D) to the deactivation of several LnIII salts and com-
plexes (Ln = Nd, Sm, Eu, Tb, Dy, Er, Yb) have been made by detailed
analysis of luminescence decay curves [142]. Data listed in Table 5
clearly point to the dramatic quenching effect of water molecules,
particularly for the NIR-emitting ions with small Eg , as well as,
for the latter, the detrimental effect of C H vibrations.
The effect of O H vibrations on both quantum yield and lifetime
serves to the determination of the number of coordinated water
molecules q, indispensable information when developing contrast
agent for magnetic resonance bioimaging. Several phenomenologi-
cal equations have been proposed, based on lifetime measurements
in water and deuterated water as well as on the assumptions that (i)
O D oscillators contribute little to deactivation and (ii) that all the
other non-radiative deactivation paths are the same in water and in
deuterated water and can henceforth be assessed by measuring the

Table 5
Quenching of LnIII luminescence by high-energy OH and CH3 vibrations: lifetimes [141] and compiled nonradiative rate constants [142] versus the energy gap. Lifetimes are
for dilute solutions of perchlorates or triflates at room temperature.

Ln Eg /cm−1 Nr of phonons Lifetime/␮s knr (OH)/ knr (CH3 )/

−1 a
OH OD H2 O D2 O s s−1 b
6
Gd( P7/2 ) 32 100 9 15 2300 n.a. n.a. n.a.
Tb(5 D4 ) 14 800 4 7 467 3800 100–200 12
Eu(5 D0 ) 12 200 3–4 5–6 108 4100 400–500 40
Yb(4 F5/2 ) 10 300 3 4.5 0.17c 3.95 3.5 × 105 3.6 × 104
Dy(4 F9/2 ) 7850 2–3 3–4 2.6 42 2 × 104 9 × 103
Sm(4 G5/2 ) 7400 2 3 2.7 60 1.8 × 104 9 × 103
Er(4 I11/2 ) 6600 2 3 n.a. 0.37 (3–5) × 108 3.3 × 106
Nd(4 F3/2 ) 5400 1–2 2–3 0.031 0.14 n.a. n.a.
a
Distance: 2.2–2.5 Å.
b
Distance: 3.6–3.9 Å.
c
Estimated from quantum yields in water and deuterated water and from  obs (D2 O).
36 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

Table 6
Phenomenological parameters for estimating hydration numbers of LnIII ions from excited state lifetime measurements in H2 O and D2 O, see Eq. (29).

Ln A B (Eu, Tb: ms; Yb: ␮s)a Accuracy Conditions Ref.

1.11 0.31 ±0.1 25 solutions, q ≤ 6 aminocarboxylates [144]

Eu 1.11 0.30 + 0.44nOH + 0.99nNH + 0.075nCONH ±0.1 8 solutions, q ≤ 3 aminocarboxylates [145]
1.2 0.25 + 1.20nNH + 0.075nCONH b
Solutions 17 q ≤ 1 and 3 q ≤ 3 cyclen derivativesc [141]

4.2 0 ±0.5 26 solutions and solids q ≤ 9 [146]

Tb
5.0 0.06 b
Solutions 13 q ≤ 1, 1 q ≤ 3 cyclen derivativesc [141]

Yb 1.0 0.20 b
11 solutions 10 q ≤ 1, 1 q ≤ 3 cyclen derivativesc [141]
a
nx is the number of X H oscillators in the first coordination sphere or of amide groups.
b
Estimated to ±0.2–0.3.
c
Including edta and dtpa complexes.

lifetime in the deuterated solvent. When applying these equations,
it is important to make sure that quenching by solvent vibrations
is by far the most important deactivation process in the molecule.
If other temperature-dependent phenomena (e.g. phonon-assisted
back transfer or charge transfer) are operating, these relationships
become unreliable. This has often been observed with TbIII [143].
The general form of these relationships is:
q = A × (kobs − B) with
(29)
kobs = kH2 O − kD2 O = 1/(H2 O) − 1/(D2 O)
where A and B are phenomenological Ln-depending (and somewhat
ligand-depending) parameters determined using series of com-
pounds with known hydration numbers. Parameter A describes the
inner-sphere contribution to the quenching, parameter B, which
has the same units as k, contains both the outer-sphere con-
tribution of closely diffusing solvent molecules and a corrective
factor accounting for the presence of other deactivating vibra-
tions, e.g. N H or C H vibrations in the vicinity of the LnIII ion.
If these X H groups have exchangeable hydrogen atoms, lifetime
will be lengthened upon D substitution; amide O CN H oscillators
also contribute to radiationless deactivation, but to a lesser extent.
The most reliable experimental relationships for H2 O are given in
Table 6, along with an estimate of their accuracy and the conditions
under which they have been determined. They are phenomenolo-
gical relationships so that it is very important to use them with
the same type of compounds for which they were calibrated and
for q values not exceeding the calibration range. The smaller q is,
the more precise the determination is. Strongly H-bonded water
molecules may also have smaller quenching effect (see next sec-
tion).
Less convincing and more empirical relationships based on
the sole measurement of H2 O have been suggested for poly-
aminocarboxylates and for NdIII , SmIII , EuIII , TbIII , and DyIII [147].
Using the equations described in Table 6 with  obs (D2 O) set equal
to the observed lifetime measured on the hydrated sample at 77 K is
also dubious because it is not granted that all vibrational quenching
is switched off at this temperature. Finally, establishing q for NdIII is
really problematic; two equations have been described [148,149]
which have to be used with care because other vibrations also
de-activate the excited levels, in particular C H vibrations and large
corrections have to be implemented.
The best way to minimize vibration-induced deactivation pro-
cesses is to design a rigid metal-ion environment, devoid of
high-energy oscillators and protecting the LnIII ion from solvent
interaction. Such an environment contributes to reduce collision-
induced deactivation in solution. Further protection may be gained
by inserting the luminescent edifice into micelles, a strategy used
in bioanalyses [150].
3.2. Influence of weak intermolecular interactions
Curiously, the presence of water molecules in the inner coor-
dination sphere does not always lead to important quenching.
Recent reports have indeed demonstrated a considerable weaken-
ing of the quenching ability of O H vibrations if the coordinated
water molecules are involved in strong intra- or inter-molecular
H-bonding. This has been invoked for a series of polymeric metal-
organic frameworks Ln(H2 O)8 ⊂[Ln2 (L20)4 ] (Scheme 6): two LnIII
ions are located at the vertices of a cage formed by the four
1,2,4-triazole-bridged bis(carboxylate) ligand while [Ln(H2 O)8 ]3+
is encapsulated in the resulting cavity. When the NdIII edifice is
treated with a EuIII solution, the central NdIII ion is exchanged for
EuIII and emission from [Eu(H2 O)8 ]3+ is seen because the bound
water molecules strongly interact with the cage (H O· · ·H and
H N· · ·H), which reduces their quenching ability [151].
TbIII is less sensitive to quenching by O H oscillators than
other LnIII ions thanks to its larger energy gap and several TbIII
complexes and metal-organic frameworks featuring metal-bound
water molecules in the inner coordination sphere display intense
luminescence. Some examples are given in Table 7, the most aston-
ishing being compounds with ligands L21–L23 which have an
overall quantum yield >80% despite two bonded water molecules
per TbIII ion. In all these compounds, bound water molecules are
involved in a complex network of H-bonds. The more important
quenching role of water molecules for EuIII compared with TbIII
is exemplified in [Tb2 (L22)(H2 O)4 ]∞ : after undergoing thermal
treatment at 120 ◦ C, the quantum yield of the TbIII metal-organic
framework increases from 89% to 96%, while similar treatment of
the EuIII compound leads to an improvement from 31% to 77%.

Table 7
Examples of highly luminescent TbIII coordination polymers with bound water molecules in the first coordination sphere. See Scheme 6 for chemical formulae of the ligands.

Complex E(1 S)/cm−1 E(3 T)/cm−1  obs /msa L

QLn /%a Ref.

[Tb(L21)3(H2 O)2 ]∞ n.a. n.a. n.a. 90 [154]

[Tb2 (L22)(H2 O)4 ]∞ n.a. n.a. 1.33 89 [155]
[Tb2 (L23)6 (H2 O)4 ]∞ 30 220 23 640 1.02 82 [156]
[Tb(L24)6 (H2 O)4 (DMF)]∞ 34 840 23 300 3.0 75 [157]
[Tb(L26)3 (EtOH)(H2 O)]∞ 31 150 23 150 0.92 72 [158]
{[Tb2 (L27)2 (L28)(H2 O)2 ](DMF)}∞ n.a. n.a. n.a. 64 [159]
[Tb(L29)3 (EtOH)(H2 O)]∞ 30 580 24 510 1.16 60 [160]
[Tb(L25)3 (H2 O)2 ]∞ 31 250 23 640 0.79 59 [158]
a
For solid state samples at room temperature.
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
CO2H HO
N
N NH2 H2L20
N N
N
CO2H HL21
N CO2H
HL23
CO2H
CH3
CO2H
CO2H
H CO2H
H2L27 H2L28
Scheme 6. Carboxylic acid ligands.
In some instances, dehydration of a coordination polymer
results in lower quantum yield, e.g. in the coordination poly-
mer with benzene-1,4-dicarboxylate, [Tb2 (L28)3 (H2 O)4 ]∞ which
sees its quantum yield decrease from 43% to 26% upon
removal of the water molecules [152]. Other documented
examples are the 3-dimensional porous coordination polymers
{[Ln2 (fumarate)2 (oxalate)(H2 O)4 ]·4H2 O}∞ (Ln = Eu, Tb) which lose
their luminescent properties upon dehydration [153].
3.3. Vibrational quenching of NIR-luminescence
NIR-luminescence, e.g. from NdIII , ErIII , YbIII , has important
applications in lasers, telecommunications, security inks, and bio-
sciences. Albeit, when linked to organic ligands, which in principle
should allow easier solution processing of the complexes for fab-
ricating devices, these ions tend to have very poor quantum yields
because of vibrational quenching, mainly through C H oscilla-
tors. As a consequence, this quenching phenomenon has received
detailed attention, based on the assumption that it can be described
by dipole–dipole (Förster) mechanism [142]. Adequate modelling
has to take into account the distance between the emitting cen-
tre and the quenching oscillator, as well as the Franck–Condon
overlap between the wavefunctions of the 4f excited state and
overtones of the deactivating oscillator [161]. The distances can
be obtained either from crystallographic data or from an analy-
sis of the lanthanide-induced shifts and relaxation times in NMR
experiments [162].
A first, obvious strategy is to replace C H oscillator with C D
vibrators. Enhanced emission by deuteration of [Nd(hfa)3 (H2 O)2 ]
has been demonstrated in 1996 by Y. Hasegawa et al. [163,164],
but modelling of the phenomenon had to wait the work of W.P.
Gillin and coworkers who quantified the quenching of the lumi-
nescence in [Er(hfa)3 (H2 O)2 ] and hydrogenated and deuterated
Cs[Er(hfa)4 ] [165]. A major conclusion of this work is that if the
37
O HO2C CO2H
HO2C N N N CO2H
N
H6L22
N
CO2H CO2H
HO2C
N
R
O
O HO2C
O
H
R = Et HL25
H2L24
HCMe2 HL26
CO2H
O O
HL29
nearest-neighbour C H oscillators are the biggest contributors to
ErIII quenching (kCH = 91 ms−1 for hfa− ), in addition, C H bonds in
the subsequent coordination spheres have also to be replaced: if a
lifetime of 0.1 ms is targeted (a minimum value for applications in
telecommunications) any C H oscillator within a sphere of 20 Å of
the emitting ion has to be removed. However, full deuteration is dif-
ficult to achieve, so that it may not be a viable solution for materials
to be used in telecommunications. In the case of NdIII the situation
is even worse since the energy gap is smaller compared with ErIII ,
kCH increases to 600 ms−1 for hfa− [166]. Halogenation instead of
deuteration has been proposed to remedy the situation [167] and,
indeed, fluorination or chlorination of the organic ligands yields
materials with interesting photophysical properties [161,168–170]
bringing the field of polymer waveguide amplifiers closer to practi-
cal applications [34]. Another strategy consists in inserting ErIII ions
in confined inorganic cavities such as zeolites [171,172]. Indeed, the
problem of luminescence deactivation through vibrations is so seri-
ous that perhalogenation may not be always the ultimate solution:
other relatively energetic vibrations such as C C, C O, or even C O
and C C, also induce non-negligible radiationless deactivations.
Quantitative and systematic studies on luminescence quenching
by C H vibrators have been carried out for macrocyclic complexes
with dota [141] and the cryptand (bpy·bpy·bpy) [173] (Scheme 7)
by selective deuteration of given C H groups. In the case of NdIII ,
the quenching effect of C H vibrators, although important, seems
to be less effective than in the hfa− complex mentioned above. On
the other hand, the quenching rate constant of YbIII obtained for the
axial C H located in the ring methylene groups and lying at approx-
imately the same distance from the metal ion (≈3.5–3.7 Å) is exactly
the same for both macrocyclic complexes, which casts confidence
in these determinations by two different groups on two different
systems. Representative quenching rate constants are collected in
Table 8. As a follow up of this work, highly luminescent cryptates
with fully deuterated [bpy·bpy·bpy O] (30 C D bonds) have been
38 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

Scheme 7. Ligands used in the study of the quenching of LnIII NIR luminescence and for upconversion.

isolated and the crystal structure of the LuIII compound determined
[174]. One arm of the cryptand contains N-oxide pyridine moieties
instead of pyridine groups. Solutions in CD3 CN display lifetimes of
3.3, 4.2 (mean), and 79 ␮s for NdIII , ErIII , and YbIII , respectively. In
deuterated methanol, the lifetime of the YbIII cryptate increases to
91 ␮s, corresponding to an estimated intrinsic quantum yield QYb Yb
These two examples, again, point to the importance of considering
the kinetics of energy migration when designing luminescent LnIII
compounds.
3.4. Revisiting the energy gap law

in the range 6–7%. The energy gap law is a first approximation approach to the
The detrimental effect of C H vibrations is further exempli- problem of vibrational deactivation of LnIII excited states in that
fied in a series of NdIII chalcogenides containing phenyl sulfide or harmonic oscillators are taken into consideration and, moreover,
selenide and dimethyl ether, pyridine, or tetrahydrofuran solvation usually one “major” vibration is introduced into the following equa-
molecules; in this series, the number of NdIII ions increases from tion, the one with the largest energy, ωmax :
1 to 8 and 17. As a result, the number of C H oscillators per NdIII
knr = A · e−(B·Eg /ωmax ) (30)
ion, nCH/Nd , decreases from 20 to 12.8 and 10.8; in addition some
oscillators are positioned further away from the metal centre. This The parameters A and B are empirical and fitted to the char-
translates into the quantum efficiency QNd Nd increasing from 9 [175]
acteristics of the system under study. The approach is indeed
to 16 [176] and 35% [177], respectively. A further modification of oversimplified for the following reasons: (i) anharmonicity of the
the molecular design leading to the cluster (py)10 Nd7 Se21 (HgSePh) oscillator should be introduced, (ii) compounds sometimes have
Nd = 43% [178]. The latter
confirms the trend: nCH/Nd = 8.5 and QNd more than one quenching vibrational modes, and (iii) since LnIII ions
yield is still substantially lower than the one observed for Nd(4 F3/2 ) have numerous electronic levels, more careful consideration of var-
in La2 S3 glass, which is near unity at low activator concentration ious resonances between energy differences and vibrational modes
[179], but this systematic work demonstrates the necessity of min- should be made. Another approach has therefore been proposed,
imizing the number of C H oscillators in the surrounding of the the “inductive-resonant” mechanism: transfer from the excited
NIR-emitting ion if high performances are sought. LnIII level is assumed to principally occur through dipole–dipole
On the other hand, some coordination compounds with ligands interaction (Förster’s energy transfer) [183]. The nonradiative deac-
not or minimally halogenated have surprisingly good NIR-emitting tivation rate constant is then expressed as [184]:
properties, for instance [Er(L30)3 ] (Scheme 7) in which intersystem 161.9 · kr · 2
crossing in the ligand is as fast as 1011 s−1 while 3 T-to-Er(4 I11/2,13/2 ) knr = × SOI (31)
2 · n4 · NA · r 6
transfer occurs with kET = 1010 s−1 ; the isc process is unexpectedly
fast and efficient, which cannot be explained on the sole basis of with kr being the radiative rate constant,  is an orientation factor
the heavy-atom effect and which opens interesting perspectives with isotropic limit equal to 2/3, n is the refractive index, NA Avo-
[180]. As a matter of fact, thin films of ErIII 8-hydroxyquinolinate gadro’s number, and r the distance between the LnIII ion and the
[Er(Q)3 ] display NIR-to-Vis ErIII upconversion [181]. Another recent oscillator; finally SOI is a Franck–Condon spectral overlap of the
breakthrough is the demonstration of ErIII upconversion in a molec- form:

ular trinuclear bimetallic helicate with an non-deuterated organic
ligand in which a sequential energy transfer operates between the SOI = In (˜) · εvibr (˜) · ˜ −4 d˜ (32)
two long-lived excited CrIII ions and the sandwiched ErIII ion [182].
In is the normalized emission spectrum expressed in energy units
Table 8 and εvibr is the molar absorption coefficient of the implied vibra-
Selected rate constants for the quenching of NdIII , ErIII , and YbIII luminescence by tion. Several parameters featured in Eqs. (31) and (32) are very
C H oscillators. Refer to Scheme 7 for chemical formulae. difficult to either calculate or determine experimentally. Neverthe-
Complex Oscillator Distance/Å kXH /ms−1 Ref. less, C. Doffek et al. [184] have recently proposed a comprehensive
approach to this problem, using Morse functions and estimates
Cs[Nd(hfa)4 ] C H 4.7 600 [166]
of SOI based on the recording of vibrational overtone spectra.
[Nd(bpy·bpy·bpy)] CH2 (eq) 3.6 73 [173] Experimental data come from the deuterated [bpy·bpy·bpy O]
CH2 (ax) 4.4 22 [173]
cryptates the structures of which have been apprehended through
CH(ar) 5.5 3.9 [173]
lanthanide-induced shift analysis. The work is quite involved and
Cs[Er(hfa)4 ] C H 4.7 91 [165] detailed but the calculated deactivation rates kobs = 1/ obs for NdIII
C D 4.7 2.4 [165]
(3.5 × 105 s−1 ), ErIII (2.5 × 105 s−1 ), and YbIII (1.1 × 104 s−1 ) per-
[Yb(dota)]− Axial ring C H 3.7 11 [141] fectly match the experimental values. Quenching rate differences
NCH2 CO n.a. 13 [141]
between the various C (H/D) oscillators have also been deciphered.
[Yb(bpy·bpy·bpy)] CH2 (eq) 3.5 12.8 [173] In turn these differences allowed the authors to explain why if
CH2 (ax) 42 11.0 [173] PrIII ⊂[bpy·bpy·bpy] is deuterated on the pyridine rings, the faint
CH(ar) 5.4 4.3 [173]
luminescence from the 1 D2 level is not improved ( obs = 157 ns
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
for 2 deuterated rings, vs 150 ns without deuteration): a negative
kpy = −45 ms−1 is calculated while benzyl oscillators behave nor-
mally, with kb = +788 ms−1 . The explanation lies in the fact that
the second harmonic of the C D vibrations (∼6900 cm−1 ) almost
perfectly matches the energy gap (∼7000 cm−1 ), in contrast to the
first overtone of the C H vibration (∼6200 cm−1 ) [185].
The new approach considering not only the smallest energy
gap between the emissive level and the next-lower sub-level of
the receiving manifold, but energy gaps matching overtone ener-
gies is revealing more adequate, for instance for SmIII for which
4G 6 nd overtone
5/2 – F9/2 corresponds exactly to the energy of the 2
of a C H vibration and of the 3rd overtone of a C D oscillator. A
similar situation prevails for DyIII (4 F9/2 –6 F5/2 ) and the model can
of course be extended to the other emitting LnIII ions [186].
4. Can the radiative lifetime be tuned?
sens
Rewriting equation (12) to explicit the overall quantum yield:
L Ln
QLn =
sens · QLn (33)
shows that both quantities on the right hand side must be opti-
mized to get highly luminous compounds. Optimization of the
sensitization efficiency has been dealt with in Section 2 while
the preceding section was concerned with maximizing the second
Ln , by minimizing vibrational de-activation. However, look-
term, QLn
ing back into Eqs. (6)–(10), it becomes clear that we have another
handle for tuning the intrinsic quantum yield: the radiative life-
time associated with the emitting electronic level. This lifetime
essentially depends on two features, the refractive index and the
composition of the inner coordination sphere of the luminescent
ion [63].
If we focus on EuIII (5 D0 ), Eq. (10) points to an n−3 dependence,
meaning that even small variations in the refractive index can
result in relatively large differences in  rad , as reflected in Table 2
for Na3 [Eu(dpa)3 ]: the radiative lifetime increases from 2.6 ± 0.2 to
4.1 ± 0.3 ms in going from the solid-state sample (n = 1.517) to the
aqueous solution (n = 1.338), in line with the estimated increase
 rad (H2 O) =  rad (sol.) × (1.517/1.338)3 = 2.6 × 1.46 = 3.8 ± 0.3 ms
[56]. A similar dependence has been demonstrated for Yb(2 F5/2 )
[57]. Therefore doping a luminescent compound into a matrix with
relatively large refractive index will decrease its radiative lifetime
and provided all other radiative and nonradiative deactivation
paths remain the same, the intrinsic quantum yield will become
larger. A LnIII complex with organic ligands has commonly n ∼ 1.5,
so that if doped into inorganic matrices such as Y2 O3 (n = 1.9),
YAl5 O12 (YAG, 1.8), YVO4 (2.0), or SrTiO3 (2.4) one may expect a
decrease in  rad of about 50, 40, 60, and 75% with concomitant
increase in QLn Ln . In addition, diluting the sample often leads to
less concentration quenching. With organic matrices, the range
of available refractive indices is more limited, e.g. for the popular
PMMA, n = 1.49, but the beneficial dilution effect remains, in
addition to energy transfer from the matrix itself, depending on
the polymer.
The influence of the chemical environment is more intricate
to decipher. Conceptually, the more mixing into the 4f-orbitals,
the less forbidden will the f–f transitions be. That is, one should
try to implement strong and polarizable bonds. Systematic stud-
ies relating  rad to the coordination environment of the LnIII ion are
still scarce. One example deals with 9-coordinate mononuclear and
dinuclear EuIII complexes with coordination environments Nx O9−x
essentially arising from benzimidazole pyridine carboxylate lig-
ands [63]. Valence-bond analysis of the available crystal structures
points to a larger contribution from the O-donor atoms compared
with the N-donor atoms and indeed, the radiative lifetime varies in
the series N3 O6 (2.7 ms) < N4 O5 (3.3 ms) < N6 O3 (4.7 ms). Although
39
this is in line with the short radiative lifetime in ␤-diketonates (with
O6 N2 or O8 chemical environments) one would have expected a
larger covalent contribution from the softer N-donor atoms. More-
over a clear relationship between  rad and the nephelauxetic effect,
as estimated from the energy of the 5 D0 →7 F0 transition, could not
be evidenced. For YbIII complexes, a similar trend is observed with
 rad (N3 O6 ) = 0.83 ms and  rad (N6 O3 ) = 0.93 ms. It is evident that
more experimental data and theoretical calculations are needed
to clarify this point.
5. Highly luminescent LnIII -containing coordination
compounds
The design of highly luminescent compounds must compel
with several requirements which may be different depending on
the emission spectral range and on the end use of the mate-
rial. Molecular designers will of course try to optimize both
and QLn Ln by finding the antenna most suitable for the targeted
III
Ln ion and by tailoring a rigid coordination environment, devoid
of high-energy vibrations. The latter aspect is of highest impor-
tance in the case of NIR-emitting ions as described above. In
addition, specific needs are required for specific applications. For
instance, luminescent materials for light-emitting diodes, solar
energy conversion, telecommunications, or luminescent coatings
should display high thermal stability and easy processing (if pos-
sible, solution processing), while luminescent bioprobes should be
both thermodynamically stable and kinetically inert in live environ-
ment and, at the same time, they should be non-cytotoxic, unless
destruction of cancerous cells is desired. Solubility may also be an
important issue.
In the following tables, we list selected highly luminescent
coordination compounds reported in the literature. Comparison is
not always easy in view of the heterogeneity of the reports and,
sometimes, the scarcity of experimental details. Moreover, deter-
mination of quantum yields is a real conundrum and many artefacts
may interfere. The most reliable ways are the comparative method
(with, ideally, two standards) and the absolute method using an
integrating sphere, but in any case, it is difficult to reach accuracy
better than 10%, even if reproducibility is good. Regarding solutions,
the comparative method requires optically dilute samples: A < 0.05,
or A < 0.5 if both sample and reference are excited at the same
wavelength, otherwise a correction for inner-filter effect has to be
applied; in turn dilute solutions have the disadvantage of favouring
complex dissociation, a fact rarely taken into account, particularly
when highly coordinating solvents such as DMSO or DMF are used.
Stability constant determination should be carried out in parallel
to photophysical investigation when dealing with solutions.
5.1. Visible-emitting ions
Table 9 reports overall quantum yields for the emission of
PrIII , SmIII , EuIII , TbIII (also see Table 7), and DyIII that are the
most commonly used ions in visible-emitting probes and mate-
rials. It is noteworthy that several LnIII ions emit both in the
visible (up to 750 nm) and in the NIR, so that the classifica-
tion made here is somewhat arbitrary. Several types of samples
are included in Table 9: solid-state samples, solutions, disper-
sions in PMMA and in hybrid materials. Most of the researchers
designing visible-emitting LnIII -based materials commonly turn to
red-emitting EuIII and green-emitting TbIII complexes since the
luminescence of these ions is less affected by the presence of
high-energy vibrators, and, consequently, they present the largest
quantum yields.
An amazing series of various antennae have been designed
and shown to work pretty well, including the simplest ones:
40 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

Table 9
Selected overall quantum yields of visible-emitting LnIII complexes at room temperature; see Schemes 1, 6 and 8 for ligand formulae. For TbIII , see also Table 7.
L
Compound State/solvent ex /nm QLn /%a Ref.

[Pr(hfa)3 (pyz)2 ] CHCl3 340 1.3 [187]

[Pr(S2 CNEt2 )3 (phen)] CH3 CN 362 0.9(5) [188]
[Pr2 (L31)3 ] H2 O + 1% CH3 CN 361 0.22 [189]
[Pr(Tf2 N)3 ] Bmpyr Tf2 N 444 0.13(3)b [190]
[Pr(L32)3 (HNOct3 )3 ] MeOH 322 1 × 10−2 [191]
[Pr(tta)3 (H2 O)2 ] DMSO 410 6 × 10−3 [192]

[Sm2 (L42)(DME)2 ]∞ Solid 330 17 [193]

[Sm2 (L33)3 (phen)] CH3 CN 334 13 [194]
[Sm(S2 CNEt2 )3 (phen)] CH3 CN 356 11(2) [188]
Sm IL Al (8.3%) c Solid 304 10 [195]
[Sm(L32)3 ](HNOct3 )3 MeOH 322 6.6 [191]
[Sm(dbm)3 (phen)] Solid n.a. 5.7(6) [196]
{Sm2 (L37)2 (L28)(H2 O)2 }·DMF Solid 280 5.2 [159]
NBu4 [Sm(L1)] Solid 330 3.4(5) [197]

Eu IL Al (9.5%) c Solid 303 96 [195]

[Eu(tta)3 (DBSO)] Solid 370 85 [86]
[Eu(L35)3 ] Solid 254 80 [198]
[Eu(tta)3 (DBP)] 1% in PMMA 405 80 [199]
[Eu(hfa)3 (DPEPO)] PMMA (% n.a.) 340 85 [200]
[Eu(nta)3 (DMSO)2 ] Solid 400 75 [201]
[Eu(L36)3 ] Solid 330 71 [97]
[Eu(L44)3 ] d MeOH 360 55 [202]

[Tb(L37)3 ] Solid 254 100 [198]

[Tb(L38b)]− H2 O n.a. 95 [203]
[Tb2 Cl6 (␮-bpy)(py)6 ]∞ Solid 310 86 [204]
[Tb(NO3 )3 (bpm)2 ] Solid 336–338 80(1) [205]
[Tb(L39)] H2 O 350 61 [206]

Dy IL Al (9%) c Solid 298 47 [195]

[Dy(L40)(phen)(H2 O)4 ]Cl·5H2 O Solid 325 19.0 [207]
[Dy(ppi)3 (DPEPO)] Solid 275 12(2) [208]
[Dy(L43)phen(OH)]∞ Solid 365 11 [209]
[Dy(NO3 )3 (L41)] CH3 CN/CHCl3 350 7.6 [210]
[Dy(L32)3 ](HNEt3 )3 H2 O 322 7.1 [191]
K3 [Dy(NTA)2 (H2 O)] Solid 325 6.3(2) [211]
[Dy(NO3 )3 (bpm)2 ] Solid 336–338 5.1(1) [205]
a
Whenever available, experimental errors are given between parentheses.
b Pr
QPr (excitation in f–f transition).
c
Hybrid material: (LnW10 O36 )9− IL@Al2 O3 , IL = 1-methyl-3-propionyloxy imidazolium bromide; % corresponds to the mol% of Ln polyoxometalate.
d
This complex has an amazingly large luminosity: 31 350 cm−1 M−1.

in solid state QLn L as high as 100% was obtained for TbIII ben-
zoate [198] or 80–85% for EuIII ternary ␤-diketonates [86,200].
Apart from ␤-diketonates, known for being highly luminescent,
benzimidazole-substituted pyridine-2-carboxylic acids HL36
(Scheme 8) can also serve as efficient sensitizers of EuIII lumines-
cence with quantum yields up to 71% in solid state and 52% in
CH2 Cl2 solution [97].
In water, overall quantum yields are usually much lower:
for EuIII , top QLnL values lie in the range 20–30%, for exam-
ple, for complexes with dipicolinate [212] or ditopic ligands
with bis(benzimidazole)pyridine core [213], or “pybox” deriva-
tives [214]. For TbIII the best values of overall quantum yield
in water are usually around 60% [206] although QLn L as high as
95% has been reported for a TbIII polyaminocarboxylate fitted
with a 4-carbamoyl-substituted pyridine antenna H4 L38b [203]
but this performance has never been confirmed nor matched.
In order to increase luminescence efficiency, LnIII complexes can
be inserted into polymer matrices [158,199,215], essentially for
decreasing energy migration between luminescent ions (con-
centration quenching). Interesting increases in luminosity are
documented: for example, the EuIII complex with a carbazole-
substituted ␤-diketone sees its quantum yield increasing from 47%
in CH2 Cl2 solution to 84% in PMMA matrix [215]. Similarly, to over-
come the problem of lower quantum yields in aqueous solutions,
LnIII complexes can be inserted into micelles or nanoparticles: QEuL
between 55% and 75% have been obtained in this way [216–219]
(this aspect is not covered in this review). One simple chromophoric
ligand worth mentioning is 2,2 -bipyrimidine (bpm) which
sensitizes the luminescence of EuIII , TbIII , and DyIII to a large extent:
[Ln(NO3 )3 (bpm)2 ] feature quantum yields of 70, 80, and 5.1%,
respectively [205].
SmIII and DyIII complexes exhibiting orange/red and yel-
low/green emission, respectively, are less luminescent, and the
highest quantum yields only reach 17% for the dimeric SmIII com-
plex with L42 [193] or 19% for a ternary DyIII oxydiacetate complex
with phenanthroline in solid state [207]; however, an amazing 47%
yield has been recorded for the inorganic–organic hybrid mate-
rial Dy IL Al (9%) [195]. In aqueous solutions, quantum yields for
these ions are small [71,220–224] and usually reach only a few
percent. The largest values are reported for complexes with H3 L39
(Scheme 8): 1% (SmIII ) and 3% (DyIII ) [206]. Another example of the
benefit obtained by using polymers is revealed by [Dy(NO3 )3 L41],
which exhibits a quantum yield of 7.6% in CH3 CN/CHCl3 [210].
The design of other visible-emitting coordination compounds
with PrIII (450–750 nm), HoIII (640 and 975 nm) or TmIII (480 nm)
is even more challenging. Quantitative data for such complexes
are occasional and values of QLn L do not exceed 1% even for
solid-state samples. The largest values reported to date for PrIII
are for [Pr(hfa)3 (pyz)2 ] (1.3% in CHCl3 ) [187] and a ternary
dithiocarbamate in CH3 CN (0.9%) [188]. In aqueous solution, the
tris(␤-diketonate) [Pr2 (L31)3 ] has QLn L = 0.22%, which can be
further increased 2.7-fold upon addition of tri(n-octyl)phosphine
oxide [189]. The two other ions have quantum yields lower than
0.1%: 1×10−2 % (HoIII ) and 6×10−2 % (TmIII ) for [Ln(L32)3 (HNOct3 )3 ]
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 41

R O OH
N HO O O
N N
HO OH
N N N
O O H2L31 O O
N N
H3L42

N N
N COOH
N N HOOC
N N H2L32 COOH
N N HOOC
N H H N
R=H H4L38a O O
CHONH2 H4L38b HO OH
O O O O
F F N O O
H2L43
F F Ar
HN NH NH
F F
O O O
H2L33
PO(OH)Me
CO2H OH OH HO Me(HO)OP N
N N
N O O O
N N
HO2C CO2H HN HN NH Ar
N
H3L34 N H3L44
H3L39
O
Ar PO(OH)Me
HOOC O COOH OMe
OH
H2L4
HL35 0 Ar = MeO

0.66x 0.34x OMe

C8H17
N O NH
HO2C N
D D D D
(CH2)5
N O
HL36 D D
CO2H N N
HO2C CO2H
N N H2L45
N
N N
H O O
Ln N-
HL37 pyz O3N NO3 F S S F
[Ln(NO3)3L41] NO3
F O O F
N F F
N N Tf2N -
N
N
N N N+
bpm
bmpyr+
N O
O
S O
DBP DBSO DME

Scheme 8. Ligands for the design of highly luminescent visible-emitting LnIII complexes.

[191], 2×10−3 % (HoIII ) and 6×10−2 % (TmIII ) for [Ln(hfa)3 (pyz)2 ]
[187] or in the 10−5 % range for complexes with tropolonate
[225]. Deuterating the ligand and working in deuterated solvents
however increases the quantum yield by several orders of mag-
nitude: a partial quantum yield of 0.12%, with a luminosity of
30 M−1 cm−1 has been reported for the 1 G4 →3 H6 transition of
[Tm(L45)2 ](DNEt3 ) [226]. Finally, green and red emission from
ErIII is usually produced by upconversion (largest yield reported:
12% for Gd2 O2 S:ErIII (10%) under 700 W/m2 excitation) [227], or
by quantum cutting (downconversion) with yields in the range
120–190% [228] so that this ion has not been included in this
section.
In summary, present status of antenna design is such that quan-
tum yields for visible-emitting solid-state samples in the range
50–70% and 70–90% can be achieved for EuIII and TbIII , respectively;
those for SmIII and DyIII lie around 10–15%, while the quantum
yields reported for other visible-emitting ions reach only 1% for
PrIII and are much lower for the other ions.
42 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47

Table 10
Selected overall quantum yields of NIR-emitting LnIII complexes at room temperature; see Schemes 1, 8 and 9 for formulae of the ligands.
L
Complex State/solvent ex /nm QLn /%a Ref.

[Pr(tta)3 (H2 O)2 ] DMSO 410 ∼0.18 [192]

[Pr(hfa)3 (pyz)2 ] CHCl3 340 3.1 × 10−3 [187]
[Pr(L32)3 ](NHEt3 )3 H2 O 322 4 × 10−4 (2) [191]

[CrNdCr(L46)3 ]9+ Solid 751 2.7(1) [233]

NdIII ⊂(ZnII MC)b Solid 370 1.13 [234]
[Nd(L47)3 (H2 O)] THF-d8 350–395 0.52 [235]
K[Nd(L48)4 ] CH3 CN 383 0.45 [236]
[Nd(L49a)3 ] Solid 350 0.33 [237]
[K(L50)3 AlNd]+ Solid 355 0.29(1) [238]
[Nd(L32)3 ](NHOct3 )3 Solid 322 0.21(1) [191]
[Nd(L51)3 ] MeCN/MeOH 395 0.17 [239]
[Nd2 L52] H2 O 250–360 0.085c [240]

[Ho(L32)3 ](NHOct3 )3 Solid 322 1 × 10−2 [191]

[Ho(hfa)3 (pyz)2 ] Solid 340 2 × 10−3 [187]
K[Ho(L53a)4 ] DMSO 340 2.3(2) × 10−3 [225]

[Er(L54)3 ] Zn(L55)2 film 405 7d [34]

[Er(L56)3 ](NO3 )3 MeCN 290 0.19(3) [214]
[Er3 (L57a)9 ] DMSO 380 0.039(4) [241]
ErIII ⊂(ZnII MC)b Solid 370 0.036(1) [234]
[Er(L49b)3 ] Solid 350–400 0.033(5) [242]
[K(L50)3 AlEr]+ Solid 355 0.028(4) [238]
K[Er(L48)4 ] CH3 CN 387 0.021 [236]
[Er(H2 L58)]3− H2 O 260–350 4.0 × 10−5 [243]

[Tm(L59)3 ] Solid 340 0.5 [128]

[Tm(L32)3 ](NHOct3 )3 Solid 322 6 × 10−2 (4) [191]
K[Tm(L48)4 ] CH3 CN 380 5.9(2) × 10−3 [236]
K[Tm(L53a)4 ] DMSO 340 3.8(2) × 10−3 [225]

[Yb(tta-d)3 (DMSO-d6 )2 ] DMSO-d6 300–350 6.1 [244]

Na[Yb(L60)4 ] Solid 450 3.7 [57]
K[Yb(L48)4 ] CH3 CN 375 3.8 [236]
[CrYbCr(L46)3 ]9+ Solid 751 3.0(3) [233]
[Yb(L61)(CoCp)]e H2 O 430 2.5 [245]
[Yb(L57b)2 (HL57b)2 Cl] DMSO 392 1.4 [246]
[Yb(L51)3 ] MeCN/MeOH 395 0.9 [239]
[Yb(H2 L58)]3− H2 O 260–350 0.37 [243]
a
Whenever available, experimental errors are given between parentheses.
b
ZnII metallacrown: (12-MCZn -4)2 (24-MCZn -8).
c
Partial quantum yield for 4 F3/2 →4 I9/2 and 4 F3/2 →4 I11/2 transitions.
d Er
Intrinsic quantum yield QEr .
e
CoCp = (C5 H5 )Co(PO(OMe)2 )3.

5.2. Near-infrared emitting ions efficiency in the triple-stranded trinuclear helicate

In coordination chemistry, studied NIR-emitting ions are often
limited to the trio NdIII (0.86, 1.06, and 1.35 ␮m), ErIII (1.54 ␮m),
and YbIII (∼1 ␮m) because of their practical applications. However,
ions such as PrIII (0.9–1.1 and 1.5 ␮m), SmIII (0.9–1.2 ␮m), DyIII
(0.9–1.4 ␮m), HoIII (0.98–1.5 and 1.9 ␮m), and TmIII (0.78 and
1.45 ␮m) also present useful emission in the NIR range; in purely
inorganic matrices, the corresponding quantum yields can be
very high, as exemplified for TmIII in germinate glasses for laser
applications, displaying 71% NIR quantum yield for the 3 F4 (TmIII )
emission at 1.9 ␮m [229]. In this section, we concentrate on coordi-
nation compounds and have to recognize that quantum yield data
for the latter five LnIII ion are not common, particularly in view
that intrinsic instead of overall quantum yields are often reported
by use of Eq. (6), since very small QLn L are difficult to measure.
Extensive reviews have been published on LnIII NIR lumines-
cence [230–232] so that only a few selected systems are listed in
Table 10.
YbIII complexes have the highest values of overall quantum
yield because this ion has the largest energy gap. When deuteration
L reaches 6.1% for [Yb(tta-d) (DMSO-d ) ]; as a compari-
is used, QYb 3 6 2
L
son, QYb drops to 2.1% for the non-deuterated analogue and to 0.12%
for [Yb(tta)3 (H2 O)2 ] in toluene [245]. The best NdIII complexes have
quantum yield in the range 1–3% in the solid state and 0.1–0.5% in
solution; one notes here the particularly good sensitization
[CrNdCr(L46)3 ]9+ in which energy is transferred from the two
d-transition metal ions onto NdIII [233], pointing to the advantage
of such an excitation mechanism. On the other hand, several
NdIII complexes are reported having very large intrinsic quantum
yields, up to 47% for [Nd(SePh)3 ] [178]. All the other NIR-emitting
ions have quantum yields usually lower than 0.1%, with a few
exceptions such as [Tm(L59)3 ].
Ligands containing 8-hydroxyquinolinate moieties perform
very well in sensitizing luminescence of NIR-emitting ions. Thus,
quantum yields for solid state samples of [Nd(L49a)3 ] [237]
and [Er(L49b)3 ] [242] reach 0.33% and 0.033%, respectively,
while for heterodinuclear YbIII NaI chelates with benzoxazole-
substituted 8-hydroxyquinolinates QYb L is as high as 3.7% [57].
The same sensitizing moiety has been incorporated into the
ditopic ligand H2 L50 which self-assemble into trimetallic heli-
cates [K(L50)3 AlLn]+ with overall quantum yields of 0.29, 0.028,
and 1.17% for Ln = NdIII , ErIII and YbIII [238]. Complexes with
porphyrins derivatized with aromatic substituents have low-
lying triplet states (≈12 000 cm−1 for tetraphenylporphyrin) so
that they appear to be ideal for sensitizing NIR-luminescence.
Unfortunately, quantum yields remain usually low (<1% for
YbIII ), except for the complex with fluorinated porphyrin H2 L62
capped with a CoIII cyclopentadienyl derivative displaying an
amazingly large quantum yield in water (2.5%) [245]. Another
large quantum yield (∼3%) has been reported at 77 K for
 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47 43

N N OH
L46 O
N N
N
N Ln
N N N N N
O
N N
N HL51
N N K+ X
X
OH
O X
F F O
O O
F F F F X
N Al X
HL47 OH
X = H HL53a
F F Cl HL53b
O
F O O F O
N H
HL48 O
3 R N R
Br [K(L50)3AlLn]+ P P HL54
R = CONEt2 HL49a R O O R
F
F F
O F F F
N R=
Br N R
F
OH N F
S F
HL49b
F OH F F F
HL55
X
O
O
N N
L56
X N
O O
O O
NH HN N OH
X = H HL57a
N N Cl HL57b
O O
HO N HO N
N N N N OH
N O N O O
HO HO P
HO HO O
N
O O OH N
H6L52 HL59
HL60

SO3-
F
F F

N F F
N
O OH
F F
N NH N
F OR
O OH
N HN
F F R=
N
N
O
F F 4 O

(H4L58) 4-
SO3 -
H2L61 F F I
2
F Et2N O NEt2

Scheme 9. Ligands for highly luminescent NIR-emitting LnIII complexes.

[Yb(acac)(TFPP)] in methylcyclohexane glass, where TFPP is 5.3. Dual emissive ions

tetrakis(5,10,15,20-pentafluorophenyl)porpholactone [247]. Alter-
native classes of ligands able to efficiently sensitize NIR Most practical applications of LnIII luminescence are based
luminescence are azulene derivatives HL48 [236] and tropolone either on visible or NIR emission. However several ions emit both
HL53 [225] which both sensitize a whole series of NIR-emitting LnIII in the visible and NIR ranges, which may be of interest if dual
ions. properties are sought for, either in marking, i.e. the non-visible
44 J.-C.G. Bünzli / Coordination Chemistry Reviews 293–294 (2015) 19–47
emission can be used to hide some information, or in biosciences.
Recent works have called attention on SmIII [197] and DyIII [208]
and dual emission of SmIII in a dendrimer has helped improving
the reliability of live cell imaging by reducing artefacts [248].
Simultaneous data on the quantum yields of visible and NIR
emission under similar excitation conditions are very scarce for
these ions, except for two recent studies. In the first one, solid state
samples of [Ln(hfa)3 (pyz)2 ] have the following ratios between
the quantum yields for visible and NIR emission: 419 for PrIII ,
579 for DyIII , and 35 for TmIII [187]. The second study deals with
[Ln(L32)3 ]3+ and the following ratios can be calculated from the
reported data for aqueous solutions: 15 for PrIII , 12 for SmIII , 65
for DyIII , 11 for HoIII , and 40 for TmIII [191]; in this investigation,
quantum yields are reported with 15–50% uncertainties, so that the
calculated ratios bear large errors, but they point to the NIR emis-
sion being always far less intense than the visible one (Scheme 9).
6. Conclusions
Expertise in the design of adequate ligands for both coordina-
tion and luminescence sensitization of trivalent lanthanide ions
has seen a tremendous development during the past two decades.
Advances in instrumentation has helped researchers to refine their
analysis by collecting more quantitative data, lifetimes, quantum
yields, sensitization efficiencies, time-resolved spectra which, in
turn, contributes to point out latent bottlenecks and to avoid them
by smart ligand design. Potential users of visible luminescence can
simply rely on these studies to produce the targeted luminescent
molecular edifices. As pointed out in the previous sections, ligand-
excited quantum yields in excess of 50% for EuIII and 70% for TbIII
are routinely obtained while values for SmIII and DyIII are smaller,
around 10–15%, but remain sizable. The situation is somewhat
different for NIR-emitting ions. Minimization of non-radiative de-
activation processes is well understood but not yet mastered at the
experimental level and only a handful of compounds have quan-
tum yields larger than 3–5% and none >10%, despite smart designs
[34]. Therefore this aspect remains an open field much in need of
clever contributions. Inorganic–organic hybrid systems might offer
a solution.
Another facet which still needs improvement is achieving
reliable predictions of photophysical properties by theoretical cal-
culations. Much has been improved, but much remains to be done
in view of the intricate problem generated by the modelling of the
numerous energy migration paths in a given compound. This is
important because too many authors rely on too simplistic and
incorrect models to interpret their data and to tailor their lumi-
nescent systems; relative energy of electronic states is not the only
characteristic to take into account, energy migration rates are of
paramount importance and should be considered in parallel to the
energy scheme.
Altogether, given the tremendous interest in lanthanide lumi-
nescence and the burgeoning of related applications, I am confident
that more detailed attention will be given to all aspects pertain-
ing to the design of LnIII luminescent edifices and this, allied with
more quantitative experimental data gathered on the energy trans-
fer processes and radiationless de-activations, will contribute to
maintain lanthanide luminescence as indispensable tool in many
fields of materials and biological sciences.
Acknowledgments
The author acknowledges financial support from EPFL and
FJIRSM (through the CAS/SAFEA International Partnership Program
for Creative Research Teams).
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