Mixed-solvothermal Synthesis, Crystal Structure and Luminescence of a New Dinuclear Yttrium(III) Coordination Polymer with 1-D Wave-like Infinite Chains①

FENG Yu-Quan JIANG Lan-Ting XING Zheng-Zheng WANG Lu

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Mixed-solvothermal Synthesis, Crystal Structure and Luminescence of a New Dinuclear Yttrium(III) Coordination Polymer with 1-Wave-like Infinite Chains①

FENG Yu-Quan②JIANG Lan-Ting XING Zheng-Zheng WANG Lu

(473061)

A new dinuclear Y3+coordination polymer{[Y2(H2O)2(C14H8O4)3(C12H8N2)2]·3H2O}(1, C14H8O4= 2,2?-biphenyldicarboxylate, phen = 1,10-phenanthroline), has been obtained by means of a mixed-solvothermal method using ethylene glycol and water as solvent. The compound was characterized by elemental analysis, energy-dispersive X-ray spectroscopy (EDS), IR spectrum and single-crystal X-ray diffraction. The results reveal that 1 belongs to monoclinic system, space group2/with= 24.249(3),= 12.069(48),= 22.7304(08) ?,= 113.480(7)°,= 4,= 6102(2) ?3,c= 1.462 g?cm-3,(000) = 2728,= 1.968 mm-1, the final= 0.0673,= 0.1508 and= 1.085. Its structure can be regarded as a 1-coordination polymer constructed by Y3+cations, 2,2?-biphenyldicarboxylate, 1,10-phenanthroline and water molecules. The compound not only contains two kinds of organic ligands, but also exhibits interesting wave-like infinite chains and 18-MR windows with the diameter of 4.070(7)? × 5.326(9)?. The structure is further stabilized by means of O–H···O hydrogen bonds and-stacking interactions. Furthermore, the luminescent properties (including emission spectrum, CIE chromaticity coordinate and decay curve) of 1 were also investigated in the solid-state at room temperature.

mixed-solvothermal synthesis,dinuclear Y3+coordination polymer, wave-like infinite chains,luminescent properties;

1 INTRODUCTION

There has been considerable interest in rare- earth(III) coordination polymers owing to their abundant structural features and potential appli- cations in the field of optical and magnetic ma- terials[1-4]. Currently, the ligands containing aromatic carboxylate anions have been widely applied in the construction of coordination polymers, which are more conducive to produce new frameworks with interesting structural features[5-7]. This is due to the fact that the aromatic carboxylate anions own excellent coordination ability with rare-earth(III) cations and they can act as bridging and chelating ligands by means of their flexible coordination modes. Previous studies have shown that many aromatic carboxylic acids containing potential chromophores can modify or produce new optical properties once they were introduced into the rare-earth(III) coordination polymers. Moreover, the metal cations of coordination polymers containing 2,2?-biphenyldicarboxylate ligand are mainly concentrated in TM2+cations including Mn2+, Co2+, Ni2+, Cd2+,[8-10]. Accordingly, guiding by the considerations, we expected that the combination of aromatic carboxylate anions and rare-earth(III) cations could obtain new polymers with interesting structural features and optical properties. In addition, the 1,10-phenanthroline can be viewed as a rigid conjugated chelating ligand which displays good solubility and low-antibonding orbital energy. The 1,10-phenanthroline is also a kind of excellent optically active ligand because it can easily generate MLCT electronic transition. We expected that the introduction of 1,10-phenanthroline can generate new rare-earth(III) coordination polymers with interesting properties. Therefore, the ligand 1,10- phenanthroline is selected as the second ligand in the formation of rare-earth(III) coordination polymers. As part of our ongoing investigations[11-16], herein, by employing two kinds of ligands, 2,2?-biphenyl- dicarboxylate and 1,10-phenanthroline (phen), we obtained a new dinuclear Y3+coordination polymer {[Y2(H2O)2(C14H8O4)3(C12H8N2)2]·3H2O}(1). The compound possesses interesting wave-like infinite chains and adds a new member into the family of rare-earth(III) coordination polymers containing two kinds of organic ligands.

2 EXPERIMENTAL

2. 1 Instruments and reagents

Elemental analyses (C, H and N) were also performed on a Perkin-Elmer 240 analyzer. Energy- dispersive X-ray spectroscopy (EDS) analysis was performed on a FEI-Quanta-200 scanning electron microscope. Infrared spectra were recorded on a Nicolet 5700 FT-IR spectrometer (400～24000 cm-1) using KBr pellets. The luminescent properties of 1 have been measured on the FLS980-fluorescence spectrometer in the solid state at room temperature. Crystal diffraction data were collected on a Bruker SMART APEX-II CCD diffractometer equipped with a graphite-monochromated Mo-radiation (= 0.71073 ?) at 293(2) K using an-scan mode. All chemicals were of reagent grade quality obtained from commercial sources and were used without further purification.

2. 2 Synthesis of {[Y2(H2O)2(C14H8O4)3(C12H8N2)2]·3H2O}n1

2. 3 X-ray crystallographic determination

A suitable single crystal of 1 (0.32mm × 0.26mm × 0.20mm) was used for structure determination. Crystal diffraction data of 1 were collected on a Bruker SMART APEX-II CCD diffractometer equipped with a graphite-monochromated Mo-Kα radiation (λ= 0.71073 ?) at 296(2) K using an ω-φscan mode. In the range of 1.98≤q≤25.00owith –28≤h≤28, –14≤k≤14 and –18≤l≤27, a total of 15008 reflections were collected, among which 5330 were unique reflections (Rint = 0.0772). Absorption correction was applied by using the SADABS[17]. The structure was solved by direct methods and refined by full-matrix least-squares techniques on F2 using SHELX-97 package[18]. All non-hydrogen atoms were refined anisotropically and hydrogen atoms isotropically by full-matrix least-squares refinement. The organic hydrogen atoms were generated geometrically. The selected bond lengths and bond angles of 1 are listed in Table 1.

Symmetry transformation: #1: –+1, –+1, –+1; #2: –+1,, –+3/2

3 RESULTS AND DISCUSSION

3. 1 EDS and elemental analyses

The results of EDS analysis reveal that compound 1 contains the elements of Y, O, N and C. This is in good agreement with the result of X-ray structural analysis. Elemental analyses (C, H and N) were performed on a Perkin-Elmer 240 analyzer. Analysis for C66H50N4O17Y2, calculated: C, 58.77; H, 3.74; N, 4.15%. Found: C, 58.43; H, 3.96; N, 4.41%. These values are further confirmed by the results of single-crystal X-ray structural analysis.

3. 2 Infrared spectroscopy

3. 3 Crystal structure

Fig. 1. Structure of compound 1. H atoms and isolated water molecules have been omitted for clarity.Displacement ellipsoids are drawn at the 30% probability level (Symmetry code: (A) 1–,, 3/2–)

Fig. 2. Structure of the infinite wave-like chain along theaxis

Fig. 3. Structure of the 18-MR windows presented in the wave-like chain

Fig. 4. A view of the packing structure of 1 along theaxis

3. 4 Luminescent properties

Fig. 5. Emission spectrum of 1

Fig. 6. CIE (1931) chromaticity diagram for the emission spectrum of 1

Fig. 7. Decay curves of 1 at room temperature

4 CONCLUSION

In summary, a new dinuclear Y3+coordination polymer containing 1-wave-like infinite chains and two kinds of organic ligands has been obtained by means of mixed-solvothermal method. The com- pound owns interesting 1-wave-like infinite chains and 18-MR windows with the dieter of 4.071? × 5.326?. The luminescent properties reveal that 1 displays a blue emission under the optimal excitation wavelength of 298 nm and its luminescent decay value is 12.0039 ns. The compound enriches the family of rare-earth(III) coordination polymers. Its successful synthesis reveals that more Y3+coordination polymers containingmultiple types of ligands may be prepared using the mixed-solvo- thermal method.

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11 August 2017;

7 February 2018 (CCDC 1566256)

① Project supported by the National Natural Science Foundation of China (No. 21601095), the Youth Project of Nanyang Normal University (No. QN2017065) and the Opening Laboratory Project of Nanyang Normal University (No. SYKF2016075)

. Feng Yu-Quan, born in 1982. Tel: 0377-63513583, E-mail: yqfeng2008@126.com

10.14102/j.cnki.0254-5861.2011-1804