Inorganic Chemistry Communications 85 (2017) 52–55

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Inorganic Chemistry Communications

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Short communication

Synthesis, crystal structures and NIR luminescence properties of

binuclear lanthanide Schiff Base complexes
Chengri Wang, Shiqing Wang, Le Bo, Ting Zhu, Xiaoping Yang ⁎, Lijie Zhang, Dongmei Jiang,
Hongfen Chen, Shaoming Huang ⁎
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
Zhejiang Key Laboratory of Carbon Materials, Wenzhou 325035, China

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

Article history: Three binuclear lanthanide complexes [Nd2(L1)3(MeOH)]·MeOH·H2O (1) and [Ln2(H2L2)2(-
Received 9 April 2017 OAc)4]·2(CF3SO3)·MeOH·EtOH (Ln = Nd (2) and Ho (3)) were prepared using two Schiff base ligands. Interest-
Received in revised form 1 June 2017 ingly, 1 has a triple-decker structure with two lanthanide ions enclosed by three rigid conjugated Schiff base
Accepted 3 June 2017
ligands (H2L1), while 2 and 3 show nanoscale ring structures (8 × 12 × 12 Å) formed by flexible long-chain Schiff
Available online 6 June 2017
base ligands (H2L2, ~23 Å) with the lanthanide ions located in the center. Upon excitation of the ligand-centered
Keywords:
absorption bands, 1–2 and 3 show typical NIR emission spectra for Nd3+ and Ho3+ ions, respectively. In 1, the
Schiff base ligands Nd(III) centers are shielded within the decker-like structure and surrounded by chromogenic Schiff base ligands
Lanthanide complexes (energy transfer donors). Luminescence studies show that the NIR emission lifetime of 1 is longer than that of 2 in
Crystal structures solution.
NIR luminescence properties © 2017 Elsevier B.V. All rights reserved.

Self-assembled polynuclear lanthanide (III) complexes have recently
attracted much attention because of their potential use in materials sci-
ence and as probes in biology [1,2]. Most trivalent lanthanide ions ex-
hibit long-lived and line-like emission bands at characteristic
wavelengths. Recently, attention has focused on the complexes of
Yb(III), Nd(III) and Er(III) with the near-infrared (NIR) emission around
900–1600 nm, which is highly transparent to biological systems and
fibre media, because of their potential applications in bioassays and lu-
minescent probes [3–10]. The photophysical properties of Ln(III) ions
depend on their ligand environments which can be designed to protect
the metal center from solvent molecules which can quench emissions.
However, the high coordination numbers and flexible coordination ge-
ometries of lanthanide ions impose a challenge to the control over the
stoichiometries and structures of polynuclear lanthanide complexes.
The structures of lanthanide complexes are often influenced by a variety
of factors such as ligand structures and the nature of counter ions.
Our recent studies have focused on the synthesis of polynuclear lan-
thanide complexes with salen type Schiff base ligands. In past studies, it
has been found that rigid conjugated Schiff base ligands with phenylene
backbones, such as H2La (Scheme 1) tended to form “multi-decker”
polynuclear lanthanide complexes [11,12], while the use of Schiff base
ligands with flexible carbon-carbon backbones, for example, H2Lb–d
(Scheme 1), resulted in a variety of polynuclear 4f and 3d-4f complexes
[13–15]. It has been found that the (CH2)n chain lengths of these flexible
⁎ Corresponding authors.
E-mail addresses: xpyang@wzu.edu.cn (X. Yang), smhuang@wzu.edu.cn (S. Huang).
ligands may affect the structures of the d-f complexes. For example, the
use of H2Le (Scheme 1) with a flexible 6 carbon backbone resulted in the
formation of two series of 24-and 32-metal Cd-Ln complexes [16]. We
were naturally interested in the influence of increasing the (CH2)n
chain length on the construction of polynuclear lanthanide complexes.
Thus we design a Schiff base ligand N,N′-bis(3-
methoxysalicylidene)heptane-1,7-diamine (H2L2, Scheme 1), which
has a 7 carbon backbone (Scheme 1). As part of our continuing studies
focused on the construction of luminescent polynuclear Ln based frame-
works, we describe here the synthesis, structures and photophysical
properties of three binuclear complexes [Nd2(L1)3(MeOH)]·MeOH·H2O
(1) and [Ln2(H2L2)2(OAc)4]·2(CF3SO3)·MeOH·EtOH (Ln = Yb (2) and
Ho (3)) with Schiff base ligands bis(3-methoxysalicylidene)ethylene-
1,2-phenylenediamine (H2L1) and N,N′-bis(3-
methoxysalicylidene)heptane-1,7-diamine (H2L2). H2L1 is a rigid conju-
gated ligand, while H2L2 is a flexible long-chain ligand. All 1–3 display
the typical emission spectra of lanthanide ions. Interestingly, with the
Ln(III) centers enclosed within the decker-like structure, 1 shows better
NIR luminescence properties than 2.
The Schiff-base ligands H2L1 and H2L2 were synthesized from the re-
actions of 3-methoxyl-2-hydroxyl-benzaldehyde with o-
phenylenediamine and heptane-1,7-diamine in refluxing ethanol, re-
spectively. Reaction of H2L1 with Nd(OAc)3·4H2O in refluxing MeOH
in the presence of Et3N gave the triple-decker complex 1. A view of
the crystal structure of 1 is shown in Fig. 1. Each Nd(III) ion is
sandwiched between two Schiff base ligands which are virtually parallel
to each other, and has eight-coordinate pseudo-square based

http://dx.doi.org/10.1016/j.inoche.2017.06.003
1387-7003/© 2017 Elsevier B.V. All rights reserved.
 C. Wang et al. / Inorganic Chemistry Communications 85 (2017) 52–55
Scheme 1. (a) Conjugate Schiff base ligands; (b) Flexible Schiff base ligands.
antiprismatic geometry. Nd(1) is bound to O2O2 and N2O2 cavities of
two Schiff-base ligands, while Nd(2) is bound to two N2O2 cavities of
the ligands. There is one H2O molecule coordinated with Nd(2), which
may affect the luminescence properties of the lanthanide ion. Two
Nd(III) ions are linked by two phenolic oxygen atoms, and the Nd-Nd
separations is 3.879 Å. The central Schiff base ligand shows a different
coordination mode from two outer ones. For example, the methoxy ox-
ygen atoms of the central ligand are monodentate, while those of outer
ligands are not coordinated with the metal ions. Also, the phenolic oxy-
gen atoms of the central ligand are bridging, while those of the outer li-
gands are monodentate. In 1, the central ligand is virtually planar while
the outer two ligands display a curved bowl-like configuration. The di-
hedral angles between these rings range from 127.3 to 153.2°. A similar
ligand arrangement was observed in the Tb multidecker complexes
[Tb3(La)4]+ and [Tb3(La)3]3+ [11]. Intramolecular π-π stacking interac-
tions between phenylene units are found in 1. The distances between
adjacent aryl units range from 3.755 Å to 4.028 Å.
Reactions of H2L2 with Ln(OAc)3·4H2O (Ln = Nd and Ho) in
refluxing MeOH/EtOH produced yellow solutions from which the
binuclear complexes 2 and 3 were isolated as pale yellow crystalline
solids. The complexes crystallize as the dication [Ln2(H2L2)2(OAc)4]2+
along with two CF3SO− 3 acting as the counter anions. 2 and 3 are isomor-
phous, and a view of the cation structure of 2 is shown in Fig. 2. The
complex 2 shows a ring structure formed by two Schiff base ligands
with lanthanide ions located in the center. Two Nd(III) ions have similar
nine-coordinate environments and each is surrounded by nine oxygen
atoms from two Schiff base ligands and four OAc− anions. The Nd(1)-
Nd(2) separation is 4.051 Å, which is longer than that in 1. For the
four OAc− anions, two are bidentate and the others are tridentate. In a
linear configuration the length of H2L2 is approximately 23 Å. This ap-
pears to increases the flexibility of the ligand and aids in the formation
of large metal complexes. Complexes 2 and 3 are of nanoscale propor-
tions. For example, the X-ray crystallographic data reveal that the mo-
lecular dimensions of 2 are approximately 8 × 12 × 12 Å. A panoramic
Fig. 1. A view of the crystal structure of 1.
53
scanning electron microscopy (SEM) image shows the crystalline na-
ture of 2 (Fig. 3a). Energy dispersive X-ray spectroscopy (EDX) analysis
of 2 indicates that the Nd:S ratio is about 1:1, in agreement with the
crystal structure (Fig. 3b). Unlike the Schiff base ligands in 1, H2L2 is
neutral and its nitrogen atoms do not bond to the metal ions in 2.
Also, intramolecular π-π stacking interactions between phenylene
units are not found in 2. The average distances for Ln-O(phenolic)
(2.268 Å (1), 2.406 Å (2), 2.328 Å (3)), Ln-O(methoxy) (2.835 Å (1),
2.680 Å (2), 2.639 Å (3)) and Ln-N (2.477 Å (1)) are comparable to
those found in the literature [17–19]. The packing structures of 1 and
2 are shown in Figs. S3 and S4, respectively.
The photophysical properties of lanthanide ions depend markedly
on the environment surrounding the metal centers. For example, unco-
ordinated solvent molecules containing O\\H and C\\H groups may
quench the luminescence of lanthanide ions through the non-radiative
exchange of electronic energy of Ln3 + to the high vibrational modes
of OH and CH groups, and their quenching efficiency decreases as the
distance Ln3+⋯Solvent increases [20]. The photophysical properties of
1–3 were studied in CHCl3 and the solid state. The free ligands H2L1
and H2L2 exhibit absorption bands at 223, 279, 331 nm and 222, 260,
328 nm, respectively, which are red-shifted upon co-ordination to
metal ions in the complexes (Fig. 4). For each complex, the lumines-
cence spectrum in the solution is similar to that in the solid state, indi-
cating the complex remains the same structure in solution as in the
solid state. Upon excitation of the ligand-centered absorption bands, 1
and 2 show typical NIR emission spectra for Nd3+ (4F3/2 → 4Ij/2 transi-
tions, j = 9, 11 and 13) (Figs. 5 and 6), while the free ligand either
H2L1 or H2L2 does not exhibit NIR luminescence under similar condi-
tions. The emission lifetime (τ) of 1 is 2.19 μs, which is longer than
that of 2 (τ = 1.32 μs). This difference may due to the fact that the
Fig. 2. A view of the crystal structure of 2.
54 C. Wang et al. / Inorganic Chemistry Communications 85 (2017) 52–55
Fig. 3. (a) The SEM image of 2; (b) The EDX spectrum of 2.
central metal ions in 1 are encapsulated in the triple-decker structure
and better shielded from solvent interactions than those in 2. Also, the
excited state energy levels of the conjugate Schiff base ligand H2L1
may be more suitable for the ligand-to-metal-energy-transfer (LMET)
than those of the flexible Schiff base ligand H2L2, which results in this
difference. The intrinsic quantum yields (ΦLn) of Nd3+ emission in 1
and 2 are calculated as 0.88% and 0.53%, respectively, using ΦLn = τ /
τ0 (τ0 = 250 μs, the natural lifetime of Nd3+ [21]). Excitation spectrum
of 1 shows one excitation band at 310 nm, while that of 2 shows two
bands at 295 nm and 405 nm (Figs. 5 and 6), in agreement with their ab-
sorption spectra, confirming that the energy transfers from the Schiff
base ligands to Nd3+ ions occur.
Compared with the NIR luminescence of some lanthanide ions com-
monly used to study, such as Yb(III), Nd(III) and Er(III), those of Ho(III)
are less well studied [22]. It is noticed that, upon excitation of the li-
gand-centered absorption bands, 3 exhibits NIR emission bands of
Ho3 + at 978, 1191 and 1476 nm originating from the 5F5 → 5I7, 5I6
→ 5I8 and 5F5 → 5I6 transitions, respectively (Fig. 6). The emission life-
time (τ) of 3 is 0.82 μs in CHCl3, which is comparable to those found
in the literature [23]. The intrinsic quantum yield (ΦLn) of Ho3+ emis-
sion in 3 is calculated as 0.02%, using ΦLn = τ / τ0 (τ0 = 5390 μs, the nat-
ural lifetime of Ho3 + [24]). As the complex 2, 3 also shows two
excitation bands at 312 nm and 408 nm (Fig. 6), in agreement with its
absorption spectrum, indicating that the Schiff base ligands can act as
efficient sensitizers for the lanthanide luminescence.
In summary, three binuclear lanthanide complexes 1–3 were con-
structed using rigid conjugated and flexible long-chain Schiff base li-
gands. 1 has a triple-decker structure, while 2 and 3 show nanoscale
Fig. 4. UV–Vis spectra of the free ligands (H2L1 and H2L2) and complexes 1–3 in CHCl3 at
298 K.
ring structures (8 × 12 × 12 Å). The structure of 1 features intramolec-
ular π-π stacking interactions between salen ligands, while these inter-
actions are not found in the structures of 2 and 3. Upon excitation of the
ligand-centered absorption bands, 1–2 and 3 show typical NIR emission
spectra for Nd3+ and Ho3+ ions, respectively. In 1, the Ln(III) centers are
surrounded by chromogenic Schiff base ligands (energy transfer do-
nors) and shielded from solvent molecules which can quench lantha-
nide emissions, while the nanoscale ring structures of 2 and 3 are
more open and the Ln3+ ions are considerably more exposed to poten-
tial interactions with solvent molecules. Luminescence studies show
that the NIR emission lifetime of 1 is longer than that of 2. Further stud-
ies focused on the construction of luminescent complexes with even
higher nuclearity using Schiff base ligands are in progress.
Acknowledgments
The work was supported by the National Natural Science Foundation
of China (No. 51025207).
Appendix A. Supplementary material
Experimental and characterization details, additional figures and ta-
bles. CCDC reference numbers 1542716-1542718. See http://www.rsc.
org/suppdata/cc/ for crystallographic data in CIF format. Supplementary
data associated with this article can be found in the online version, at
doi: http://dx.doi.org/10.1016/j.inoche.2017.06.003.
Fig. 5. Excitation and emission spectra of 1 in CHCl3.
 C. Wang et al. / Inorganic Chemistry Communications 85 (2017) 52–55
Fig. 6. Excitation and emission spectra of 2 and 3 in CHCl3.
References
[1] J.-B. Peng, Q.-C. Zhang, X.-J. Kong, Y.-Z. Zheng, Y.-P. Ren, L.-S. Long, R.-B. Huang, L.-S.
Zheng, Z. Zheng, High-nuclearity 3d-4f clusters as enhanced magnetic coolers and
molecular magnets, J. Am. Chem. Soc. 134 (2012) 3314–3317.
[2] B. Wang, Z. Zang, H. Wang, W. Dou, X. Tang, W. Liu, Y. Shao, J. Ma, Y. Li, J. Zhou, Mul-
tiple lanthanide helicate clusters and the effects of anions on their configuration,
Angew. Chem. Int. Ed. 52 (2013) 3756–3759.
[3] J.W. Stouwdam, G.A. Hebbink, J. Huskens, F.C.J.M.V. Veggel, Lanthanide-doped nano-
particles with excellent luminescent properties in organic media, Chem. Mater. 15
(2003) 4604–4616.
[4] J.-C.G. Bünzli, Metal Ions in Biological Systems, 42, Ed. M. Dekker, New-York, 2004.
[5] L. Chen, H. Zhang, M. Pan, Z.-W. Wei, H.-P. Wang, Y.-N. Fan, C.-Y. Su, An efficient vis-
ible and near-infrared (NIR) emitting SmIII Metal–organic framework (Sm-MOF)
sensitized by excited-state Intramolecular proton transfer (ESIPT) ligand, Chem.
Asian. J. 11 (2016) 1765–1769.
[6] M. Pan, B.-B. Du, Y.-X. Zhu, M.-Q. Yue, Z.-W. Wei, C.-Y. Su, Highly efficient visible-to-
NIR luminescence of lanthanide(III) complexes with Zwitterionic ligands bearing
charge-transfer character: beyond triplet sensitization, Chem. Eur. J. 22 (2016)
2440–2451.
[7] L.-Y. Zhang, Y.-J. Hou, M. Pan, L. Chen, Y.-X. Zhu, S.-Y. Yin, G. Shao, C.-Y. Su, Near-in-
frared (NIR) emitting Nd/Yb(III) complexes sensitized by MLCT states of Ru(II)/
Ir(III) metalloligands in the visible light region, Dalton Trans. 44 (2015)
15212–15219.
[8] S.-R. Zheng, R.-L. Chen, Z.-M. Liu, X.-L. Wen, T. Xie, J. Fan, W.-G. Zhang, Construction
of terpyridine–Ln(III) coordination polymers: structural diversity, visible and NIR lu-
minescence properties and response to nerve-agent mimics, CrystEngComm 16
(2014) 2898–2909.
55
[9] H. Sun, L. Wu, W. Yuan, J. Zhao, Y. Liu, Phenoxo-O bridged dinuclear lanthanide com-
plexes based on a multitooth Schiff base ligand: structures, fluorescence properties
and single-molecule magnet behavior, Inorg. Chem. Commun. 70 (2016) 164–167.
[10] N. Henry, M. Lagrenee, F. Abraham, Solvothermal synthesis, a new preparative route
to mononuclear lanthanide complexes with in situ built N4O2 hexadendate Schiff
base. Synthesis and crystal structure of N,N′-bis[(2-
salicylideneamino)ethyl]ethane-1,2-diamine nitrato[O,O]Erbium(III) hydrate,
Inorg. Chem. Commun. 11 (2008) 1071–1074.
[11] X.-P. Yang, R.A. Jones, Anion dependent self-assembly of “tetra decker” and “triple-
decker” luminescent Tb(III) salen complexes, J. Am. Chem. Soc. 127 (2005)
7686–7687.
[12] X.-P. Yang, R.A. Jones, W.-K. Wong, Pentanuclear tetra-decker luminescent lantha-
nide Schiff base complexes, Dalton Trans. 2008 (1676–1682).
[13] W.-K. Lo, W.-K. Wong, W.-Y. Wong, J. Guo, K.-T. Yeung, Y.-K. Cheng, X.-P. Yang, R.A.
Jones, Heterobimetallic Zn(II)-Ln(III) phenylene-bridged Schiff base complexes,
computational studies, and evidence for singlet energy transfer as the main path-
way in the sensitization of near-infrared Nd(III) luminescence, Inorg. Chem. 45
(2006) 9315–9325.
[14] X.-P. Yang, R.A. Jones, W.-K. Wong, V. Lynch, M.M. Oye, A.L. Holmes, Design and syn-
thesis of a near infra-red luminescent hexanuclear Zn-Nd prism, Chem. Commun.
2006 (1836–1838).
[15] X.-P. Yang, C. Chan, D. Lam, D. Schipper, J.M. Stanley, X. Chen, R.A. Jones, B.J. Holliday,
W.-K. Wong, S.C. Chen, Q. Chen, Anion-dependent construction of two hexanuclear
3d-4f complexes with a flexible Sciff base ligand, Dalton Trans. 41 (2012)
11449–11453.
[16] X.-P. Yang, D. Schipper, R.A. Jones, L. Lytwak, B.J. Holliday, S.-M. Huang, Anion de-
pendent self-assembly of NIR luminescent 24- and 32-metal Cd-Ln complexes
with drum-like architectures, J. Am. Chem. Soc. 135 (2013) 8468–8471.
[17] N.C. Anastasiadis, D.A. Kalofolias, A. Philippidis, S. Tzani, C.P. Raptopoulou, V.
Psycharis, C.J. Milios, A. Escuer, S.P. Perlepes, A family of dinuclear lanthanide(III)
complexes from the use of a tridentate Schiff base, J. Chem. Soc. Dalton Trans. 44
(2015) 10200–10209.
[18] C. Camp, V. Guidal, B. Biswas, J. Pecaut, L. Dubois, M. Mazzanti, Multielectron redox
chemistry of lanthanide Schiff-base complexes, Chem. Sci. 3 (2012) 2433–2448.
[19] M. Andruh, Compartmental Schiff-base ligands-a rich library of tectons in designing
magnetic and luminescent materials, Chem. Commun. 47 (2011) 3025–3042.
[20] N. Sabbatini, M. Guardigli, J.M. Lehn, Luminescent lanthanide complexes as photo-
chemical supramolecular devices, Coord. Chem. Rev. 123 (1993) 201–228.
[21] S.I. Klink, L. Grave, D.N. Reinhoudt, F.C.J.M.V. Veggel, A systematic study of the
photophysical processes in polydentate triphenylene-functionalized Eu3+, Tb3+,
Nd3+, Yb3+, and Er3+ complexes, J. Phys. Chem. A 104 (2000) 5457–5468.
[22] M. Sakamoto, K. Manseki, H. Okawa, d–f Heteronuclear complexes: synthesis, struc-
tures and physicochemical aspects, Coord. Chem. Rev. 219 (2001) 379–414.
[23] C.Y. Chow, S.V. Eliseeva, E.R. Trivedi, T.N. Nguyen, J.W. Kampf, S.P. Petoud, V.L.
Pecoraro, Ga3+/Ln3+ metallacrowns: a promising family of highly luminescent lan-
thanide complexes that covers visible and near-infrared domains, J. Am. Chem. Soc.
138 (2016) 5100–5109.
[24] S. Dang, L. Sun, H. Zhang, X. Guo, Z. Li, Z. Guo, Near-infrared luminescence from sol-
gel materials doped with holmium(III) and thulium(III) complexes, J. Phys. Chem. C
112 (2008) 13240–13247.