Journal of Molecular Structure 1137 (2017) 27e32

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Synthesis, crystal structures, photoluminescent, magnetic and

chiroptical properties of two homochiral ErIII complexes with different
nuclearity
Xi-Li Li*, Ying-Fan Liu, Xue-Li Zhang, Conghui Cheng, Xianjun Zheng, Cancan Zhu,
Liming Zhou**
Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, PR China

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

Article history: Employing chiral bis-bidentate N-donor ligand, (þ)-2,5-bis(4,5-pinene-2-pyridyl) pyrazine (L), as a
Received 19 September 2016 bridging ligand for Er(dbm)3H2O, and depending on the ratio control of reactants, two mono- and
Received in revised form dinuclear homochiral ErIII complexes with the formulae Er(dbm)3L$2H2O (1) (dbm
5 February 2017 e
¼ dibenzoylmethanate) and Er2(dbm)6L$6H2O (2) have been synthesized and structurally character-
Accepted 8 February 2017
Available online 10 February 2017
ized. Circular dichroic (CD) spectra verify their chiroptical activities. Investigations on the luminescent
properties of complexes 1 and 2 demonstrate that they exhibit characteristic near-infrared (NIR) lumi-
nescence of the ErIII ion at around 1533 nm and the emission intensity of the mononuclear complex 1 is
Keywords:
Homochiral ErIII complexes
much larger than that of dinuclear species 2, the reason of which is elucidated in this work. In addition,
Near-infrared luminescence the measurements of magnetic properties indicate that the direct-current (dc) magnetic behaviors of
Magnetic property complexes 1 and 2 mainly result from the thermal depopulation of the excited MJ sublevels of the ErIII
Chiroptical property ions. Notablely, complex 2 is the first example of chiral polynuclear lanthanide complexes with NIR-
Control of metal nuclearity luminescence property.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction in laser systems, biomedical analysis, optical amplification and

The exploitation of lanthanide complexes is a hot topic of
research due not only to their particular photophysical properties
[1,2] but also to their interesting magnetic behaviors stemming
from the unique f electronic configurations of lanthanide ions
[3e5]. Regarding their luminescent features, lanthanide complexes
usually display element-specific emission, long lifetimes, large
stokes shifts and sharp emission bands, making them of particu-
larly attractive for applications in display devices, tunable lasers,
luminescent probes in biology and efficient photo-conversion
molecular devices [6e9]. In this context, considerable efforts have
been concentrated on the EuIII and TbIII-based species emitting in
the visible range, whereas the NdIII, ErIII and YbIII-containing ana-
logs with near-infrared (NIR) luminescent properties are less
developed. Recently, NIR-luminescence lanthanide complexes have
gained increasing attention because of their promising applications
* Corresponding author.
** Corresponding author.
E-mail addresses: lixl@zzuli.edu.cn (X.-L. Li), zlming1212@126.com (L. Zhou).
telecommunication networks [10e17]. Especially, the NIR- lumi-
nescence of ErIII-doped materials is of significant because the
emission at about 1.53 mm matches the spectral region used in
long-distance optical fiber telecommunications [18]. However, it is
difficult to observe intense luminescence by direct excitation of
lanthanide ions due to very low molar absorption coefficients
originating from their Laporte-forbidden fef transitions. An effec-
tive strategy of sensitizing the emission of lanthanide ions is
employing organic chromophores as an “antenna” for light har-
vesting, thereby exciting the emission of lanthanide ions indirectly.
b-diketones have been proven to be a class of effective ‘‘antenna’’
ligands for sensitizing the lanthanide ions owing to the following
attributes: (1) They have a small energy gap between the lowest
singlet (S1) state and the triplet (T1) state, favoring to transfer
efficiently the energy to the lanthanide ions [19e23]; (2) They
possess a high affinity to the lanthanide ions, forming stable
lanthanide complexes for practical applications [24]. As a result, a
lot of mononuclear ErIII b-diketonate complexes with NIR-
luminescence property have been obtained [11,16,25e30]. Among
them, only three cases are based on dbme diketonate ligand

http://dx.doi.org/10.1016/j.molstruc.2017.02.027
0022-2860/© 2017 Elsevier B.V. All rights reserved.
28 X.-L. Li et al. / Journal of Molecular Structure 1137 (2017) 27e32

(dbme ¼ dibenzoylmethanate) [16,27,30]. However, as far as we 2.2. Synthesis

know, there only two dinuclear ErIII b-diketonate complexes,
Er2(nd)6bpm (nd ¼ 2,4-nonanedione, bpm ¼ bipyrimidine) [31] 2.2.1. Synthesis of Er(dbm)3L,2H2O (1)
and Er2(HTH)6bpm (HTH ¼ 4,4,5,5,6,6,6-heptafluroro-1- (2- A solution of Er(dbm)3H2O (89 mg, 0.1 mmol) in ethanol (10 mL)
thienyl)hexane-1,3-dione) [32] with NIR-luminescence property was added to a solution of (þ)-2,5-bis(4,5-pinene-2-pyridyl)pyr-
have been documented so far. azine (L) (42 mg, 0.1 mmol) in acetone (10 mL) with gentle stirring
In addition to their unique luminescence performance, lantha- for 20 min at room temperature. Subsequently, the mixture was left
nide b-diketonate complexes with chirality may display fascinating undisturbed for two weeks. The block pink crystals of complex 1
physical properties such as circularly polarized luminescence (CPL), were obtained in 82% yield (based on Er). Elemental Anal. calc. for 1
second harmonic generation (SHG), magneto-chiral dichroism (C73H67ErN4O8): C, 67.67; H, 5.21; N, 4.32. Found: C, 67.59; H, 5.17;
(MChD) effect and ferroelectricity [33e38], being potential multi- N, 4.26%. Main IR peaks (KBr pellet, cm1): 1605 (s, nC]O stretch-
functional molecule-based materials. To obtain chiral lanthanide b- ing), 1549 (s, nC]N stretching).
diketonate complexes, the most effectual method is the use of N-
containing chiral organic ligands that directly introduce the chiral
information into the resultant molecular materials. In this study,
we have synthesized a chiral bis-bidentate N-donor ligand (þ)-2,5- 2.2.2. Synthesis of Er2(dbm)6L,6H2O (2)
bis(4,5-pinene-2-pyridyl)pyrazine (L, Scheme 1). It possesses two A solution of Er(dbm)3,H2O (180 mg, 0.2 mmol) in ethanol
sets of N,N-chelating sites separated by a rigid heterocycle spacer (15 mL) was added to a solution of (þ)-2,5-bis(4,5-pinene-2-pyr-
and each set of chelating sites is able to coordinate to the metallic idyl)pyrazine (L) (42 mg, 0.1 mmol) in acetone (10 mL) with gentle
ions depending on the ratio control of reactants. Employing it as a stirring for 30 min at room temperature. Subsequently, the mixture
bridging ligand to react with Er(dbm)3H2O, two mono- and dinu- was placed undisturbed for one week. The block pink crystals of
clear ErIII complexes with the formulae Er(dbm)3L$2H2O (1) and complex 2 were isolated in 79% yield (based on Er). Elemental Anal.
Er2(dbm)6L$6H2O (2) were obtained based on the ratio control of calc. for complex 2 (C118H96Er2N4O18): C, 64.64; H, 4.41; N, 2.56.
reactants. They exhibit characteristic NIR-luminescence of the ErIII Found: C, 64.57; H, 4.38; N, 2.51%. Main IR peaks (KBr pellet, cm1):
ion at 1533 nm and the emission intensity of the mononuclear ErIII 1608 (s, nC]O stretching), 1552 (s, nC]N stretching).
complex 1 is much larger than that of dinuclear species 2. Notably,
complex 2 represents the first example of polynuclear chiral
lanthanide complexes with NIR-luminescence property. Herein, we
reported the syntheses, crystal structures together with chiroptical 2.3. X-ray data collection and structure determination
activities, NIR-luminescence and magnetic properties of complexes
1 and 2 in detail. The X-ray single crystal data of complexes 1 and 2 were
collected on a Bruker SMART APEX CCD diffractometer with
graphite monochromated Mo Ka radiation (l ¼ 0.71073 Å) at room
2. Experimental temperature using both F and u scan modes. Data reductions were
made with the Bruker SAINT package. Absorption corrections were
2.1. Material and physical measurements performed using the SADABS program. The structures were solved
by direct methods and refined on F2 by full matrix least-squares
All reagents and chemicals are commercially available and used using SHELXL-97 with anisotropic displacement parameters for
without further purification. Er(dbm)3H2O was prepared according all non-hydrogen atoms. H atoms were introduced in calculations
to reference's method [39]. (þ)-2,5-bis(4,5-pinene-2-pyridyl)pyr- using the riding model. All computations were carried out using the
azine (L) were synthesized according to reported procedures [40]. SHELXTL-2000 program package. Detailed crystallographic data
Elemental analyses for C, H and N were performed on a Vario EL III and structures refinement parameters for complexes 1 and 2 are
Elemental analyzer. The IR spectra were registered on a TENSOR27 summarized in Table 1, and selected bond lengths and angles are
Bruker Spectrophotometer from KBr pellets in the region of listed in Table 2.
4000e400 cm1. Excitation and emission spectra were measured
on Edinburgh FLS920 fluorescence spectrophotometer at room
temperature. Solid-state CD spectra were recorded on a JASCO J-810 Table 1
Crystallographic data and structure refinement parameters for 1 and 2.
spectropolarimeter from KCl pellets (1% wt.) at room temperature.
Magnetic susceptibility measurements were carried out on crys- 1 2
talline samples with a Quantum Design MPMS superconducting Chemical formula C73H67ErN4O8 C118H96Er2N4O18
quantum interference device (SQUID) magnetometer in the tem- Formula weight 1295.57 2192.51
perature range of 2.0e300 K. Diamagnetic corrections were carried Crystal system Orthorhombic Monoclinic
Space group P212121 P21
out considering both the sample holder as the background and the
a (Å) 17.1319 (3) 13.8059 (3)
diamagnetism of the constituent atoms estimated from Pascal's b (Å) 18.0555 (3) 20.9177 (5)
constant. c (Å) 21.7184 (4) 18.7408 (5)
a ( ) 90 90
b ( ) 90 105.494 (3)
g ( ) 90 90
V (Å3) 6718.0 (2) 5215.4 (2)
Z 4 2
3
Dc (g/cm ) 1.281 1.396
1
m/mm 1.305 1.667
GOF 1.024 1.029
R1a/wR2b 0.0473/0.1051 0.0505/0.0808
Flack parameter 0.024 (9) 0.027 (10)
a P P
R1 ¼ jjFojjFcjj/ jFoj.
b P P
Scheme 1. Chemical structure of the chiral bis-bidentate bridging ligand (L). wR2 ¼ [ w(Fo2Fc2)2/ w(Fo2)2]1/2.
 X.-L. Li et al. / Journal of Molecular Structure 1137 (2017) 27e32 29

Table 2 bound by six oxygen atoms of three dbme anions and two nitrogen
Selected bond lengths (Å) and angles ( ) for 1 and 2. atoms from the chiral ligand (L), forming an ErN2O6 polyhedral
Bond lengths for 1 core. Only one of the two sets of N-donor chelating sites within the
Er(1)eO(1) 2.280 (4) Er(1)eO(4) 2.354 (4)
chiral ligand takes part in the coordination. The EreO bond lengths
Er(1)eO(2) 2.310 (4) Er(1)eO(5) 2.323 (4) range from 2.280(4) to 2.354(4) Å, while the lengths of the two
Er(1)eO(3) 2.281 (4) Er(1)eO(6) 2.312 (4) EreN bonds are 2.537(5) and 2.570(5) Å, respectively. A detailed
Er(1)eN(1) 2.537 (5) Er(1)eN(4) 2.570 (5) analysis of coordination geometry indicates that the two faces
Bond angles for 1 defined by O3eO4eO6eO5 and O1eO2eN1eN4 are creased about
O(1)eEr(1)O(3) 89.11 (14) O(3)eEr(1)O(4) 71.92 (14) the respective diagonals O3eO6 and O2eN4 with angles of 25.4
O(3)eEr(1)O(2) 91.85 (15) O(6)eEr(1)O(4) 73.26 (15) (4) and 13.5 (6). The corresponding angles are 0 and 0 for a
O(3)eEr(1)N(1) 146.46 (14) O(6)eEr(1)N(4) 82.01 (15) square antiprism, 29.5 and 29.5 for a dodecahedron, and 21.8
Bond lengths for 2 and 0 for a bicapped trigonalprism geometry [41]. Hence, the co-
ordination geometry of central ErIII ion in 1 is close to a bicapped
Er(1)eO(1) 2.303 (8) Er(1)eO(4) 2.290 (7)
Er(1)eO(2) 2.251 (8) Er(1)eO(5) 2.290 (6) trigonal prism (Fig. S1), while the O4 and O5 atoms cap the two
Er(1)eO(3) 2.268 (8) Er(1)eO(6) 2.302 (9) quadrilateral faces composed of O2eO3eO6eN1 and O1eO3e
Er(1)eN(1) 2.579 (10) Er(1)eN(2) 2.545 (8) O6eN4, respectively.
Er(2)eO(7) 2.282 (10) Er(2)eO(10) 2.313 (8)
Er(2)eO(8) 2.268 (7) Er(2)eO(11) 2.314 (8)
Er(2)eO(9) 2.262 (8) Er(2)eO(12) 2.304 (9) 3.1.2. Crystal structure of 2
Er(2)eN(3) 2.588 (10) Er(2)eN(4) 2.582 (8) Complex 2 has two octacoordinate ErIII ions bridged by the bis-
Bond angles for 2 bidentate N-donor ligand (L) and separated by 7.929 Å (Fig. 2),
O(2)eEr(1)O(3) 96.0 (3) O(4)eEr(1)O(5) 143.9 (3) which is apparently longer than that of analog (7.011 Å) bridged by
O(3)eEr(1)O(4) 73.2 (3) O(2)eEr(1)O(1) 73.0 (3) 2,20 -bipyrimidine (bpm) [42]. In contrast to complex 1, two
O(3)eEr(1)N(1) 70.1 (3) O(6)eEr(1)N(2) 77.8 (3) chelating sites of the N-donor ligand (L) in complex 2 are occupied
O(8)eEr(2)O(7) 73.2 (3) O(7)eEr(2)O(11) 75.3 (3) by two ErIII ions, while each ErIII ion has the same coordinate atoms
O(9)eEr(2)O(10) 72.4 (3) O(12)eEr(2)O(11) 72.2 (3)
O(8)eEr(2)N(3) 70.0 (3) O(11)eEr(2)N(4) 78.7 (3)
as those of 1 (O6N2). For Er1 atom, the average lengths of the Er1eO
and Er1eN bonds are 2.284 Å and 2.562 Å, respectively. These
values are almost equal to those of Er2 atom (2.290 and 2.585 Å for
average Er2eO and Er2eN, respectively). Each ErIII ion is in an
3. Results and discussion
octacoordinate environment in complex 2 with two approximate
geometry planes defined as N1eN2eO4eO3 and O1eO2eO5eO6
3.1. Structural description
for Er1 atom, and N3eN4eO11eO12 and O9eO10eO8eO7 for Er2
atom (Fig. S2). The creased angles of two approximate planes for
X-ray crystallographic analyses reveal that complexes 1 and 2
Er1 atom are 15.1 (0.6) and 11.1 (0.5), and the creased angles for
crystallize in respective P212121 and P21 space groups with chiral
Er2 atom are 23.4 (0.6) and 22.0 (0.5). Therefore, Er1 atom and its
crystal structures, suggesting that chirality deriving from chiral bis-
bound atoms adopt a geometry that can be best described as an
bidentate N-donor ligand has been transferred into the solid
intermediate between square antiprism and dodecahedron,
structures of complexes 1 and 2, respectively.
whereas Er2 atom along with its bound atoms adopt a geometry
that is close to a dodecahedron. Although two ErIII centers have the
3.1.1. Crystal structure of 1 same bound atoms (O6N2) in 2, it is noteworthy that they present
As shown in Fig. 1, complex 1 is a mononuclear ErIII complex and different coordination geometries probably due to both large steric
the asymmetric unit of 1 contains an Er(dbm)3 moiety, a chiral N- hindrances of dbme ligands and non-centrosymmetric molecular
donor ligand (L) and two lattice water molecules. The ErIII ion is

Fig. 1. ORTEP representation (50% probability ellipsoids) of 1 from a viewpoint that Fig. 2. ORTEP representation (50% probability ellipsoids) of 2 from a viewpoint that
emphasizes the chiral structures; for clarity, only the ipso C atoms of each aromatic emphasizes the chiral structures; for clarity, only the ipso C atoms of each aromatic
ring are shown and H atoms along with lattice water molecules are omitted. ring are shown and H atoms along with lattice water molecules are omitted.
30 X.-L. Li et al. / Journal of Molecular Structure 1137 (2017) 27e32
arrangements [43].
3.2. Circular dichroic (CD) spectra
To prove the chiroptical activities of complexes 1 and 2, their
solid-state CD spectra were measured. As shown in Fig. 3, complex
1 exhibits positive Cotton effect at lmax ¼ 302 nm with negative
Cotton effects at lmax ¼ 250 and 373 nm (Fig. 3a). Complex 2 ex-
hibits positive Cotton effects at lmax ¼ 286 and 371 nm with
negative ones at lmax ¼ 240 and 328 nm (Fig. 3b). The results show
that the profiles of their CD spectra are similar because of the same
organic chromophores within respective molecular structure. The
bands between 200 and 300 nm at high energy are assigned to the
p/p* transitions of the chiral bis-bidentate N-donor ligand (L),
while the bands over 300 nm at low energy can be ascribed to the
p/p* transitions of the dbme diketonate ligand [39,44].
3.3. Near-infrared luminescent property
The excitation spectra of complexes 1 and 2 have been recorded
between the ranges of 350e600 nm monitoring the NIR-emission
of ErIII ion at 1533 nm at room temperature (Fig. S3). The broad
and intense excitation band in the 350e500 nm range, peaking at
around 467 nm, is associated with the intra-ligand singlet-singlet
Fig. 3. Solidestate CD spectra of 1 (a) and 2 (b) based on pressed KCl disks including
1% (wt.) of crystal grains at room temperature.
p-p* electronic transition of dbme ligand from the S0 ground to the
S1 excited state. Large wavelength of transition can be ascribed to
the presence of large conjugated systems within the molecular
structures of complex 1 and 2. Another excitation band at 520 nm
can be assigned to the characteristic absorption transition 4I15/
2 III
2 / H11/2 of the Er ion [45].
Under the identical measurement conditions, NIR-luminescence
properties of the ErIII ions in complexes 1 and 2 in the solid state
were investigated. As shown in Fig. 4, the profiles of the emission
spectra of 1 and 2 are similar because the ligands coordinated to
ErIII ions are identical and the coordination surroundings of ErIII
ions in 1 and 2 are also similar. In both cases, the emission bands
that cover large spectra range extending from 1460 to 1635 nm
show a maximum at around 1533 nm, which are attributed to the
characteristic 4I13/2 / 4I15/2 transition of the ErIII ion in the NIR
range. The results imply that such an emission profits from an
efficient energy transfer from the dbme ligand to the ErIII ion, so-
called “antenna effect.” In particular, ErIII-containing materials
have attracted much interest because the transition around
1530 nm right falls into the region of the third telecommunication
window, and a broad emission band is desirable for optical
amplification [46]. Moreover, it is noteworthy that the emission
intensity at 1533 nm for mononuclear complex 1 is much larger
than that of dinuclear species 2. The reason is that the fef energy
transfer between two ErIIIeErIII centers results in a nonradiative
decay process, which further quenches the emission intensity of
the ErIII ions in dinuclear complex 2 [47]. To the best of our
knowledge, complex 2 is the first example of chiral polynuclear
lanthanide complexes with NIR-luminescence property.
3.4. Magnetic properties
Direct-current (dc) magnetic susceptibility measurements were
performed based on polycrystalline samples of complexes 1 and 2
in the temperature rang 2.0e300 K under an applied magnetic field
of 1000 Oe. The plots of cMT versus T are shown in Fig. 5. For
complex 1, the cMT value is 12.74 cm3 K mol1 at room temperature
(Fig. 5a), which is slightly larger than the theoretical value of
11.48 cm3 K mol1 for an isolated ErIII ion (4I15/2, S ¼ 3/2, L ¼ 6,
g ¼ 6/5). The corresponding cMT value of 22.04 cm3 K mol1 for
complex 2 is close to the paramagnetic value of 22.96 cm3 K mol1
for two uncoupled ErIII ions (Fig. 5b). Upon cooling, the cMT
Fig. 4. The NIR-luminescent spectra of 1 and 2 in the solid state at room temperature.
 X.-L. Li et al. / Journal of Molecular Structure 1137 (2017) 27e32 31

Acknowledgements

The authors acknowledge the financial supports of the National

Natural Science Foundation of China (Nos. 21371156, 21471136 and
21671178).

Appendix A. Supplementary data

Supplementary data related to this article can be found at http://

dx.doi.org/10.1016/j.molstruc.2017.02.027.

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