采用溶剂热法合成出单核Zn(Ⅱ)配合物［Zn(2,6-PDA)(phen)H2O］·H2O (1)和双核Cu(Ⅰ)配合物{［Cu(μ-Ⅰ)(phen)H2O］·H2O}2 (2) (2,6-H2PDA=2,6吡啶二甲酸, phen=1,10-邻菲罗啉), 通过单晶结构测试、 元素分析和红外吸收光谱对结构进行表征, 并研究了两种配合物在二甲基亚砜(DMSO)中及固态时的荧光光谱及DMSO溶液中紫外可见吸收光谱。 配合物1和2的最大吸收峰分别出现在253和242 nm附近, 相比于配体吸收峰均发生红移, 在1和2中, 主要呈现出中心金属离子微扰的phen的π→π*的跃迁, 且吸收强度强于phen, 说明中心金属离子与phen配位后, 增加了有机配体在紫外区的吸收, 利于配体对能量的吸收。 1在DMSO溶液中的荧光发射峰位于361, 379和392 nm, 在固态时的荧光发射峰为407, 434和467 nm, 2在DMSO溶液中的荧光发射峰出现在422, 443和461 nm, 固态时荧光发射峰在442, 469, 501 nm, 均呈现蓝光发射。 配合物1和2的固态荧光发射光谱与相应的DMSO溶液中的发射峰相比分别红移55和23 nm, 这是由于在固态时配合物1和2的分子中的π—π堆积相互作用和分子间的相互作用, 特别是配合物2中存在强烈的Cu(Ⅰ)…Cu(Ⅰ)相互作用, 降低了体系前线轨道之间的能量差。

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.