| 基于吡啶基三联吡啶配体的锌（Ⅱ）和镉（Ⅱ）配合物的晶体结构和荧光性质 | |
| Zinc(Ⅱ) and Cadmium(Ⅱ) Complexes Derived from 4'-(2-Pyridyl)-2,2': 6',2″-terpyridine: Crystal Structures and Fluorescence Property | |
| 摘要: 在溶剂热条件下合成了配合物[Zn （2-pyterpy）2]（ClO4）2·0.25H2O （1）和[Cd （2-pyterpy）2]2（ClO4）4·2.33H2O·CH3OH （2）（2-pyterpy=4'-（2-吡啶基）-2，2'∶6'，2″-三联吡啶），并通过元素分析、FT-IR光谱、X射线单晶衍射和X射线粉末衍射进行了表征。X射线单晶衍射结果表明，2个配合物属于三斜晶系，P1空间群。在激发波长为405 nm时，固态配合物1和2的荧光峰分别位于539和547 nm。在甲醇溶液中，配合物1和2的激发波长分别为357和352 nm，荧光峰分别为408和371 nm；亚稳态光酸mPAH1的最佳激发波长和荧光波长分别为467和556 nm。用mPAH1滴定配合物1，则mPAH1使配合物1在408 nm处的荧光猝灭，猝灭常数KSV为2.961×104 L·mol-1，但荧光寿命基本不变，这归因于内滤效应。相反，用配合物1滴定mPAH1，则混合溶液在556 nm处的荧光增强，这归因于mPAH1使配合物1部分质子化。 | |
| 关键词: 锌（Ⅱ）配合物 镉（Ⅱ）配合物 亚稳态光酸 三联吡啶 内滤效应 | |
| 基金项目: 国家自然科学基金（No.21771111，21101096，21371104）和河北省引进留学人员资助项目（No.C20200317）资助。 | |
| Abstract: Complexes [Zn(2-pyterpy)2] (ClO4)2·0.25H2O (1) and [Cd(2-pyterpy)2]2(ClO4)4·2.33H2O·CH3OH (2) (2-pyterpy=4'-(2-pyridyl)-2,2':6',2″-terpyridine) were synthesized under solvothermal conditions, and structurally characterized by elemental analysis, FT-IR spectra, X-ray single crystal diffraction and powder X-ray diffraction. X-ray single crystal diffraction results show that they crystallize in the triclinic system with the P1 space group. In solid-state, complexes 1 and 2 showed the maxima emission band approximately at 539 and 547 nm upon excitation at 405 nm, respectively. In methanol solution, complexes 1 and 2 exhibited emissions at 408 and 371 nm upon excitation at 357 and 352 nm, respectively. The metastable-state photoacid mPAH1 showed fluorescence at 556 nm upon excitation at 467 nm. When complex 1 was titrated with mPAH1, the fluorescence of complex 1 at 408 nm was quenched by mPAH1 with a quenching constant KSV of 2.961×104 L·mol-1, but the fluorescence lifetime of complex 1 remained nearly unchanged, which is attributed to the inner filter effect. Conversely, titration of mPAH1 with complex 1 resulted in enhanced fluorescence of the mixed solution at 556 nm, which is attributed to partial protonation of complex 1 by mPAH1. | |
| Keywords: zinc(Ⅱ) complex cadmium(Ⅱ) complex metastable-state photoacid terpyridine inner filter effect | |
| 投稿时间：2022-04-17 修订日期：2022-06-06 | |
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| 苑亚南,王子璇,王朝阳,宋瑶瑶,王庆伦,杨春.基于吡啶基三联吡啶配体的锌（Ⅱ）和镉（Ⅱ）配合物的晶体结构和荧光性质[J].无机化学学报,2022,38(9):1878-1886. | |
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