Synthesis, Structure and Spectroscopy Study of a 1D Copper Coordination Polymer Based on a Carboxybenzyl Viologen Ligand and SCN-Anion
QIU Li-xia1, WAN Fang1, ZHU Bin-bin1, SUN Yan-qiong1,2*, YOU Yi1*, CHEN Yi-ping1
1. Department of Chemistry, Fuzhou University, Fuzhou 350108, China 2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
Abstract:A zwitterionic viologen derivative ligand, 1,1’-bis(4-carboxybenzyl) -4,4’-bipyridinium dichloride (H2BpybcCl2) as a multifunctional ligand, has been synthesized incorporating a 4,4’-bipyridine core with two carboxylate groups as a building block, specifically designed for the rational construction of metal-organic frameworks. H2BpybcCl2 ligand is a multifunctional ligand that contains viologen’s specific functions and carboxylate coordination groups. The coordination polymers of viologen carboxylate with copper thiocyanate are not reported to date. A novel copper coordination polymer, [Cu(SCN)2(Bpybc)] (Ⅰ) was by solution diffusion method and characterized by single-crystal X-ray diffraction, XRD, elemental analyses, IR spectroscopy, UV-Vis DRS, TG analysis and liquid-state luminescent properties. Compound Ⅰ crystallized in the monoclinic system with C2/c space group. Crystal data for complex Ⅰ is as follow: a=19.508(4) , b=9.474(2) , c=16.963(3) , α=90°, β=124.92(3)°, γ=90°. Two SCN- anions were coordinated to the Cu2+ cation forming a [Cu(SCN)2] unit. Complex Ⅰ was built up by [Cu(SCN)2] units bridged sequentially by ladder-shaped Bpybc ligands to form one-dimensional zigzag chains running along the [203] direction. The chains were held together by π—π interaction between the pyridine rings and phenyl rings, thus yielding a 3-D extended supramolecular network. The UV-Visible absorption spectra show the absorption bands of π—π* transitions of Bpybc ligands and d→d transition of Cu2+. The liquid-state luminescent property of compound Ⅰ was investigated at room temperature. Attractively, the complex exhibits strong blue emission peak at 533 nm (λEx=360 nm) that can be assigned to intraligand transition of Bpybc ligand when it was excited at 360 nm.
邱丽霞1,宛 方1,朱彬彬1,孙燕琼1,2*,游 毅1*,陈义平1 . 基于紫精羧酸和SCN-离子构建的一维铜配位聚合物的合成、结构及光谱学研究 [J]. 光谱学与光谱分析, 2015, 35(05): 1340-1344.
QIU Li-xia1, WAN Fang1, ZHU Bin-bin1, SUN Yan-qiong1,2*, YOU Yi1*, CHEN Yi-ping1 . Synthesis, Structure and Spectroscopy Study of a 1D Copper Coordination Polymer Based on a Carboxybenzyl Viologen Ligand and SCN-Anion. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(05): 1340-1344.
[1] Monk P M S. The Viologens. New York; Wiley, 1998. [2] Mercier, N. Eur. J. Inorg. Chem., 2013, 19. [3] Byrd H, Suponeva E P, Bocarsly A B, et al. Nature, 1996, 38: 610. [4] Yu Z, Yu K, Lai L L, Udachin K A, et al. Chem. Comm., 2004, 648. [5] Ito F,Nagamura T. J. Photochem. Photobiol., C, 2007, 8: 174. [6] Bose A, He P G, Liu C, et al. J. Am. Chem. Soc., 2002, 124: 4. [7] Kisch H, Eisen B, Dinnebier R, et al. Chem. Eur. J., 2001, 7: 738. [8] Jin X H, Ren C X, Sun J K, et al. Chem. Comm., 2012, 48: 10422. [9] Sun J K, Wang P, Zhang J, et al. J. Mater. Chem., 2012, 22, 12212. [10] Sun Y Q, Zhang J, Ju Z F, et al. Cryst. Growth Des., 2005, 5: 1939. [11] Sheldrick G M. Program for Empirical Absorption Correction of Area Detector Data. University of Gttingen: Gttingen, Germany, 1996. [12] Sheldrick G M. SHELXTL, Version 5.1.; Bruker Analytical X-ray Instruments Inc.: Madison, WI, 1998. [13] Lin-Vien D, Colthup N B, Fateley W G, et al. The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules. Academic Press: San Diego, 1991. [14] (a) Demchenko A P. Luminescence, 2002, 17:19; (b) Heldt J R. J. Fluoresc., 2011, 21:239.