Abstract：The mononuclear Zn(Ⅱ) complex [Zn(2,6-PDA)(phen)H2O]·H2O (1) and binuclear Cu(Ⅰ) complex{[Cu(μ-Ⅰ)(phen)H2O]·H2O}2 (2) (2,6-H2PDA=2,6- pyridinedicarboxylic acid，phen=1,10- phenanthroline monohydrate) have been prepared with hydro-thermal synthesis method. These complexes have been characterized with single-crystal X-ray, elemental analysis, and IR spectroscopy. The fluorescence spectra of 1 and 2 are studied in solid-state and dimethyl sulfoxide (DMSO) solution. The maximum absorption peak of 1 and 2 are at 253 nm and 242 nm respectively, which are red shift to that of the phen ligand with inceased intensity. It may be assigned to the intraligand π→π* transition of the phen ligand that is modified by the Zn(Ⅱ) or Cu(Ⅰ) ions. On the basis of the coordination, the absorption of organic ligands in the ultraviolet region is increased, which is better for the energy absorption of the ligand. 1 and 2 all showed blue light emission. The emission peak of 1 and 2 have experienced a red shift (ca. 55 and 23 nm) in the solid state (λem = 407, 434, 467 nm for 1, 442, 469, 501 nm for 2) compared to in DMSO solution (λem = 361, 379, 392 nm for 1, 422, 443, 461 nm for 2). The red shift phenomenon can be attributed to the π-stacking of the aromatic rings and other intermolecular Interactions in these molecules in the solid state. Especially, the strong Cu(Ⅰ)…Cu(Ⅰ) interaction of 2 can decrease the HOMO—LUMO energy gap with the red-shifted emission wavelength.
徐 阳，强亮生，范瑞清*，王 平，杨玉林* . 含氮配体构筑的单核锌Zn(Ⅱ)/双核Cu(Ⅰ)配合物蓝光材料的结构和荧光性能研究 [J]. 光谱学与光谱分析, 2016, 36(04): 996-1000.
XU Yang, QIANG Liang-sheng, FAN Rui-qing*, WANG Ping, YANG Yu-lin* . Study on the Structure and Photoluminescent Properties of Mono-Zn(Ⅱ) and Di-Cu(Ⅰ) Complexes Constructed from Nitrogen Heterocyclic Ring Ligand . SPECTROSCOPY AND SPECTRAL ANALYSIS, 2016, 36(04): 996-1000.
[1] ZHANG Ling-yun, YANG Yu-lin, FANF Rui-qing, et al(张凌云, 杨玉林, 范瑞清, 等). Chemical Journal of Chinese Universities(高等学校化学学报), 2013, 34(6): 1470. [2] Cid J J, Mohanraj J, Mohankumar M, et al. Chem. Commun., 2013, 49: 859. [3] McCann M, McGinley J, Ni K, et al. Chem. Commun., 2013, 49: 2341. [4] Vitale M, Ford P C, Coord. Chem. Rev., 2001，4: 219. [5] Jiang D, Yao R, Ji F, et al. Eur. J. Inorg. Chem., 2013, 4：556. [6] Shelxtl N T. Crystal Structure Analysis Package, Version 5.10, Bruker AXS, Analytical X-Ray System, Madison, WI，1999. [7] Harrison W T A, Ramadevi P, Kumaresan S. Acta Cryst., 2006, E62: m513. [8] Ma C, Fan C, Chen C, et al. Acta Cryst., 2002, C58: m553. [9] Knorr M, Guyon F, Khatyr A, et al. Dalton Trans., 2009, 6：948. [10] Sutton L E. Table of Interatomic Distances and Configurations in Molecules and Ions, Special Publication 18; The Chemical Society, London, 1965, 1956. [11] Zhang Z Y, Deng Z P, Zhang X F, et al. Cryst. Eng. Comm., 2014, 16: 359. [12] Wang F, Yu R M, Wu X Y, et al. Inorganic Chemistry Communications, 2012, 19: 70. [13] GAO Hong-ling, CHENG Peng(高洪苓, 程 鹏). Chinaese Jpurese of Inorganic Chemistry(无机化学学报), 2004, 20(10): 1145. [14] Wang X M, Fan R Q, Qing L S, et al. Chem. Commun., 2014, 50：5023.
