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A trinuclear bright red luminophore containing cyclometallated Ir(III) motifsw
Vadapalli Chandrasekhar,* S. M. Wahidur Rahaman, Tanima Hajra, Dipak Das,
Tapas Ghatak, Shahnawaz Rafiq, Pratik Sen* and Jitendra K. Bera*
Received 13th May 2011, Accepted 15th August 2011
Published on 25 August 2011 on http://pubs.rsc.org | doi:10.1039/C1CC12830B
DOI: 10.1039/c1cc12830b
Downloaded by Indian Institute of Technology Kanpur on 28 August 2011
The trinuclear complex [{Ir(ppy)2}3(L1)2](OTf)3 (1) is a bright
red luminophore whereas the monomer [Ir(ppy)2L2](OTf) (2)
exhibits emission in the green region.
Bis-cyclometallated IrIII complexes are characterized by their
high emission quantum efficiency, easy synthetic tuning of the
emission bands and high thermal and chemical stability.1 It is
therefore not surprising that this class of compounds is found
to be suitable for a wide range of applications including as
sensors, sensitizers, photocatalysts, biological labelling agents
and as dopants in organic light-emitting diodes (OLEDs).2
Although these studies are limited to mononuclear Ir(III)
complexes, there have been scattered attempts to explore
multinuclear analogues with an intention to achieve improved
optical characteristics.3 A diiridium compound (ppy)2Ir(m-BPB)-
Ir(ppy)2 (ppyH = 2-phenyl pyridine) bridged by a doubly-
cyclometallating ligand 1,4-bis(pyridin-2-yl)benzene (BPB) shows
a substantial red-shifted emission (ca. 150 nm) in comparison
to Ir(ppy)3.4 Unfortunately, any prospect of this compound
finding devise application is severely restricted due to its very low
yield (B3%). In contrast, Baranoff and Nazeeruddin et al. have
recently reported a neutral tetranuclear cyanide-bridged compound
[{Ir(ppy)2(CN)}4] which essentially retains the photophysical
features of its mononuclear congener [Ir(ppy)2(CN)2] .5 One
way to influence the emissive state, it appears, is to introduce
variation in the bridging ligand.6 We anticipated that nitrogen-
rich bridging ligands would perturb frontier orbitals affecting
the nature and hence the energy of the emissive states. Further,
suitably designed bridging ligands would allow an extended
structure facilitating electron delocalization and thereby lead-
ing to a red-shifted emission.
In pursuit of this objective, herein, we describe a bright red
emitter consisting of three ‘Ir(ppy)2’ units bridged by two
naphthyridine-triazole hybrid ligands L1 (Scheme 1). A mono-
nuclear compound with naphthyridine-pyrazine ancillary
ligand L2 (Scheme 1) has also been synthesized and the
electrochemical and photophysical properties of the mono-
and the trinuclear compounds are compared. The trinuclear
Department of Chemistry, Indian Institute of Technology Kanpur,
Kanpur, 208016, India. E-mail: jbera@iitk.ac.in
w Electronic supplementary information (ESI) available: Full experi-
mental, computational and X-ray details. CCDC 820921 and 820922.
For ESI and crystallographic data in CIF or other electronic format
see DOI: 10.1039/c1cc12830b
This journal is c The Royal Society of Chemistry 2011
COMMUNICATION
Scheme 1 Schematic diagrams of the ancillary ligands used.
assembly [{Ir(ppy)2}3(L1)2](OTf)3 (1) is a bright red luminophore,
distinctly different from the monomer [Ir(ppy)2L2](OTf) (2)
which exhibits emission in the green region. The red shifted
emission of the title compound 1 thus suggests a new tuning
strategy that is based on the variation of the bridging ligand
leading to multinuclear cyclometalated Ir(III) complexes.
Compound 1 was synthesized in high-yields via the self-
assembly of ‘Ir(ppy)2’ units with L1. The reaction of the
chloro-bridged dimer [{(ppy)2Ir}2(m-Cl)2], first with AgOTf to
effect dechlorination, followed by the treatment of L1 afforded
the trinuclear compound [{Ir(ppy)2}3(L1)2](OTf)3 (1). The
1
H NMR spectrum of this compound is quite complex due to the
presence of different stereoisomers in the trinuclear structure
(Fig. S1, ESIw). In a dinuclear compound, three possible isomers,
one meso (D,L) and two enantiomeric pairs (D,L and L,D) have
been identified,7 but a similar assignment proved to be difficult
for 1. Although elemental analysis indicated a 3 : 2 composition
of ‘Ir(ppy)2’ and L1, the ESI-MS showed peaks corresponding
to the mononuclear species [Ir(ppy)2(L1)]+ at m/z 726.23 and
[Ir(ppy)2(L1)(CH3CN)]+ at m/z 767.19. Similar fragmentation
has also been reported for other Ir(ppy)2 clusters.5 The structure
of 1 was unambiguously identified by X-ray crystallography.
The molecular structure of 1 consists of three organo-
metallic ‘Ir(ppy)2’ subunits that are bridged by two L1 ligands as
shown in Fig. 1. Each Ir center exhibits a slightly distorted
octahedral geometry, although the coordination environment
around the central Ir is different from the terminal Ir centers.
In addition to two cyclometallating ppy ligands (C^N), each
terminal Ir is chelate bound to L1 via the naphthyridine and
triazole nitrogens resulting in a five-membered IrN3C ring.
Thus, each terminal iridium atom is surrounded by a 2C, 4N
coordination environment contained in three chelating rings.
Four of the six coordinating sites of the central Ir are occupied
by two ppy ligands. Two triazole nitrogens from two independent
L1 ligands complete the coordination sphere. The X-ray
structure of 1 further reveals that the cis-C, C and trans-N,
N chelate disposition of the ppy ligands of the chloro-bridged
Chem. Commun.

Fig. 1 ORTEP diagram of the tricationic unit of 1 with important
Published on 25 August 2011 on http://pubs.rsc.org | doi:10.1039/C1CC12830B
atoms labeled. Hydrogen atoms are omitted for the sake of clarity.
Downloaded by Indian Institute of Technology Kanpur on 28 August 2011
precursor complex is retained in 1. The Ir1


Ir2 and Ir1


Ir3
non-bonded distances are 6.2996(8) and 6.2729(10) Å and
Ir1


Ir2


Ir3 angle is 131.3(1)1.
Compound 1 exhibits intense absorptions at 250 and 330 nm
which are assigned to spin-allowed ligand centered (1LC)
transitions involving ppy and L1 ligands, respectively
(Fig. 2). The absorption at 400 nm is attributed to a
metal-to-ligand charge transfer (MLCT) transition which is
spin allowed, and therefore more intense and at higher energy
than the weaker transition at 480 nm. Accordingly, the latter
can be assigned to a 3MLCT transition. When the dichloro-
methane solution of 1 is excited at 420 nm, a bright red
luminescence with a maximum at 685 nm is observed and
the photoluminescence quantum yield is estimated to be 0.58.
The excited state lifetime in a deaerated solution is 6.55 ms.
The cyclic voltammogram (CV) measured in acetonitrile
solution shows two oxidation processes. The first event is
reversible at E1/2 = 1.01 (80) V followed by an irreversible
oxidation at Ep, c = +1.49 V (Fig. S3, ESIw). These two
oxidations are tentatively attributed to two types of iridium
centers, the single central iridium and two terminal iridiums.
As discussed vide supra, the molecular structure of 1 reveals
different coordination environments around the central and
terminal iridium centers. Consequently, 1 exhibits oxidations
at different potentials. In addition to the oxidation events, two
irreversible reductions occur at Ep, c = 1.05 V and 1.44 V.
The first reduction is due to the bridging ligands L1 and the
second one is assigned for the cyclometallated ppy ligands. An
additional irreversible reduction wave was observed at
Fig. 2 UV-visible absorption (blue) and emission (red) spectra of 1 in
dichloromethane solution at room temperature.
Chem. Commun.
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0.16 V which was subsequently identified as a return wave
associated with the second oxidation process at +1.49 V.
Cyclometallated Ir(ppy)2 complexes with neutral N-donor
ligands emit, generally, in the blue-green region.1,8 Chemical
alteration of the ancillary ligands allows significant tuning of
the emission band.8 Nevertheless, red phosphorescent Ir(III)
complexes are intrinsically less emissive than blue and green
emitters.9 Remarkably, the trinuclear complex 1 exhibits red
luminescence with a high quantum yield. To understand the
effect of the bridging ligand and the enhanced dimensionality,
if any, on the emission behavior of 1, we synthesised a mono-
nuclear Ir(ppy)2 complex bearing naphthyridne-pyrazine
ancillary ligand L2, [Ir(ppy)2L2](OTf) (2). The molecular
structure of 2 consists of a cationic octahedral Ir complex
with four of the six coordinating sites being occupied by two
cyclometallating ppy (C^N) ligands while the remaining two
sites are occupied by the L2 chelate ligand as shown in Fig. 3.
Therefore, the Ir center is in octahedral geometry with a 2C,
4N coordination environment contained in three chelating
rings. ESI-MS reveals the molecular mass ion at m/z 709.17.
Two reversible reductions, associated with the ancillary lignd
L2 and the cyclometallating ligand ppy, are oserved at E1/2 =
0.82(70) and 1.45(80) V, respectively (Fig. S4, ESIw). The
metal based-oxidation appears as an irreversible wave at
+1.23 V.
Compound 2 exhibits multiple strong absorptions in the UV
region at 250, 268, 336 and 352 nm which are ascribed to intra-
ligand transitions located on both the ppy and L2 ligands. A
MLCT absorption appears at 400 nm extending up to 500 nm.
Compound 2 exhibits an unusually sharp green emission at 508 nm
upon irradiation at 420 nm in dichloromethane (Fig. 4). The
corresponding photoluminescence quantum yield is 0.32 and
the excited state lifetime in a deaerated solution is 1.70 ms.
The mono and tricationic units of compounds 1 and 2 were
subjected to full DFT optimization. The essential structural
parameters obtained from DFT calculations are found to be
similar to their corresponding X-ray structures (Fig. S5 and
S6, ESIw). Computed NPA charges in 1 reveal that the central
iridium is less positive (+0.738) than terminal iridium centres
(0.774, 0.775). This explains why the former is oxidized at
lower potential. Analysis of the frontier orbitals in 1 reveals
that the Ir centres are electronically isolated. The HOMO in 1
is located on one of the terminal Ir center and the ppy ligands
Fig. 3 ORTEP diagram of the cationic unit of 2 with important
atoms labeled. Hydrogen atoms are omitted for the sake of clarity.
This journal is c The Royal Society of Chemistry 2011

Published on 25 August 2011 on http://pubs.rsc.org | doi:10.1039/C1CC12830B
Fig. 4 UV-visible absorption (blue) and emission (green) spectra of 2
Downloaded by Indian Institute of Technology Kanpur on 28 August 2011
in dichloromethane solution.
chelated to it with contributions 30% and 65% respectively.
The LUMO is based on the L1 which is ligated to the same Ir,
with contributions more than 95% (see Fig. S7, ESIw). Like-
wise, the HOMO in 2 is a ppy based orbital (66%) with
significant contributions from the Ir dp orbital (32%) and
the LUMO is described as the p* orbital of L2 with contri-
butions up to 96% (Fig. S8, ESIw). The computed
HOMO–LUMO gaps for complexes 1 and 2 are 2.07 and
2.23 eV, respectively. Careful examination of the MOs failed
to identify an orbital involving contributions from multiple Ir
centers, overlapped by the symmetry matched orbitals from
L1. This clearly indicates that the bridging ligand L1 is not an
ideal electronic conduit between the metals which is in
accordance with the CV experiments. In essence, compound
1 does not exhibit significant electron delocalization through-
out the trinuclear structure which could be credited to its red-
shifted emission.
We tentatively attribute the red-shifting to the triazole-
based bridging ligand L1. Excited state calculations for the
title complex proved to be impractical because of its large
molecular size. Instead, calculations were carried out on the
diprotonated {L1
2H}2+ and monoprotonated {L2
H}+
species, wherein each protonation mimics coordination of the
positively charged ‘{Ir(ppy)2}’ unit. The double protonation of
L1 is warranted to simulate the bridging situation. Excited
state single-point energy calculations under the TD-DFT
framework reveal a low-lying triplet manifold centered on
the bridging triazole unit of {L1
2H}2+. The energy difference
between the first triplet and singlet ground state in {L1
2H}2+
is computed to be 50 nm red-shifted compared to {L2
H}+.
This clearly indicates that L1 provides a low-lying triplet
emissive state compared to L2 which is in agreement with
the longer lifetime measured for 1. It is therefore likely that the
origin of red-shifting of 1 lies in the triazole-based ligand.
Higher nuclearity creates a bridging situation for the ancillary
ligand which in turn perturbs the electronic structure. This
new paradigm requires to be further tested using a larger
ensemble of multi-topic ligands that would allow the construction
of a wide range of multinuclear Ir(III) complexes. Design and
execution of such experiments are underway.
JKB acknowledges the department of science and technology
(DST), India, for Swarnajayanti fellowship. Authors thank an
anonymous reviewer for insightful comments.
This journal is c The Royal Society of Chemistry 2011
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Notes and references
1 (a) L. Flamigni, A. Barbieri, C. Sabatini, B. Ventura and
F. Barigelletti, Top. Curr. Chem., 2007, 281, 143; (b) Y. You and
S. Y. Park, Dalton Trans., 2009, 1267; (c) W.-Y. Wong and C.-L. Ho,
Coord. Chem. Rev., 2009, 253, 1709; (d) M. S. Lowry and S. Bernhard,
Chem.–Eur. J., 2006, 12, 7970; (e) C. Ulbricht, B. Beyer, C. Friebe,
A. Winter and U. S. Schubert, Adv. Mater., 2009, 21, 4418.
2 For OLED applications, see, (a) J. D. Slinker, A. A. Gorodetsky,
M. S. Lowry, J. Wang, S. Parker, R. Rohl, S. Bernhard and
G. G. Malliaras, J. Am. Chem. Soc., 2004, 126, 2763; (b) Y. You
and S. Y. Park, Dalton Trans., 2009, 1267; (c) M. K. Nazeeruddin,
R. Humphry-Baker, D. Berner, S. Rivier, L. Zuppiroli and
M. Graetzel, J. Am. Chem. Soc., 2003, 125, 8790;
(d) M. S. Lowry, J. I. Goldsmith, J. D. Slinker, R. Rohl,
R. A. Pascal Jr, G. G. Malliaras and S. Bernhard, Chem. Mater.,
2005, 17, 5712; Biological labeling agent: (e) K. K.-W. Lo,
C.-K. Chung and N. Zhu, Chem.–Eur. J., 2003, 9, 475; (f) K. K.-W.
Lo, K. H.-K. Tsang, K.-S. Sze, C.-K. Chung, T. K.-M. Lee,
K. Y. Zhang, W.-K. Hui, C.-K. Li, J. S.-Y. Lau, D. C.-M. Ng
and N. Zhu, Coord. Chem. Rev., 2007, 251, 2292; Photocatalyst:
(g) J. I. Goldsmith, W. R. Hudson, M. S. Lowry, T. H. Anderson
and S. Bernhard, J. Am. Chem. Soc., 2005, 127, 7502;
(h) E. D. Cline, S. E. Adamson and S. Bernhard, Inorg. Chem.,
2008, 47, 10378; Sensitizer: (i) E. Baranoff, J.-H. Yum, I. Jung,
R. Vulcano, M. Grätzel and M. K. Nazeeruddin, Chem.–Asian J.,
2010, 5, 496; (j) Z. Ning, Q. Zhang, W. Wu and H. Tian,
J. Organomet. Chem., 2009, 694, 2705; Sensor: (k) M. C. DeRosa,
D. J. Hodgson, G. D. Enright, B. Dawson, C. E. B. Evans and
R. J. Crutchley, J. Am. Chem. Soc., 2004, 126, 7619; (l) Y. Amao,
Y. Ishikawa and I. Okura, Anal. Chim. Acta, 2001, 445, 177.
3 (a) T. Hajra, J. K. Bera and V. Chandrasekhar, Inorg. Chim. Acta,
2011, 372, 53; (b) F. Neve, A. Crispini, S. Serroni, F. Loiseau and
S. Campagna, Inorg. Chem., 2001, 40, 1093; (c) E. A. Plummer,
J. W. Hofstraat and L. D. Cola, Dalton Trans., 2003, 2080;
(d) F. Lafolet, S. Welter, Z. Popović and L. De Cola, J. Mater.
Chem., 2005, 15, 2820; (e) C. H. Shin, J. O. Huh, S. J. Baek,
S. K. Kim, M. H. Lee and Y. Do, Eur. J. Inorg. Chem., 2010, 3642.
4 A. Tsuboyama, T. Takiguchi, S. Okada, M. Osawa, M. Hoshino
and K. Ueno, Dalton Trans., 2004, 1115.
5 E. Baranoff, E. Orselli, L. Allouche, D. D. Censo, R. Scopelliti,
M. Grätzel and M. K. Nazeeruddin, Chem. Commun., 2011,
47, 2799.
6 (a) J. Li, P. I. Djurovich, B. D. Alleyne, M. Yousufuddin, N. N. Ho,
J. C. Thomas, J. C. Peters, R. Bau and M. E. Thompson, Inorg.
Chem., 2005, 44, 1713; (b) S. Lamansky, P. Djurovich, D. Murphy,
F. Abdel-Razzaq, R. Kwong, I. Tsyba, M. Bortz, B. Mui, R. Bau
and M. E. Thompson, Inorg. Chem., 2001, 40, 1704;
(c) M. K. Nazeeruddin, R. Humphry-Baker, D. Berner, S. Rivier,
L. Zuppiroli and M. Graetzel, J. Am. Chem. Soc., 2003, 125, 8790.
7 A. Auffrant, A. Barbieri, F. Barigelletti, J. Lacour, P. Mobian,
J.-P. Collin, J.-P. Sauvage and B. Ventura, Inorg. Chem., 2007,
46, 6911.
8 (a) M. K. Nazeeruddin, R. T. Wegh, Z. Zhou, C. Klein, Q. Wang,
F. D. Angelis, S. Fantacci and M. Grätzel, Inorg. Chem., 2006,
45, 9245; (b) M. S. Lowry, W. R. Hudson, R. A. Pascal Jr and
S. Bernhard, J. Am. Chem. Soc., 2004, 126, 14129; (c) F. Neve,
M. L. Deda, A. Crespini, A. Bellusci, F. Puntoriero and
S. Campagna, Organometallics, 2004, 23, 5856; (d) M. Lepeltier,
T. K.-M. Lee, K. K.-W. Lo, L. Toupet, H. L. Bozec and
V. Guerchais, Eur. J. Inorg. Chem., 2005, 110; (e) J. I. Goldsmith,
W. R. Hudson, M. S. Lowry, T. H. Anderson and S. Bernhard,
J. Am. Chem. Soc., 2005, 127, 7502; (f) F. Neve, M. L. Deda,
F. Puntoriero and S. Campagna, Inorg. Chim. Acta, 2006, 359, 1666;
(g) H. J. Bolink, L. Cappelli, E. Coronado, M. Grätzel, E. Ortı́,
R. D. Costa, P. M. Viruela and M. K. Nazeeruddin, J. Am. Chem.
Soc., 2006, 128, 14786; (h) F. D. Angelis, S. Fantacci, N. Evans,
C. Klein, S. M. Zakeeruddin, J.-E. Moser, K. Kalyanasundaram,
H. J. Bolink, M. Grätzel and M. K. Nazeeruddin, Inorg. Chem.,
2007, 46, 5989; (i) K. A. King and R. J. Watts, J. Am. Chem. Soc.,
1987, 109, 1589.
9 H. Tsujimoto, S. Yagi, H. Asuka, Y. Inui, S. Ikawa, T. Maeda,
H. Nakazumi and Y. Sakurai, J. Organomet. Chem., 2010,
695, 1972.
Chem. Commun.