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

在溶剂热条件下合成了配合物[Zn(2-pyterpy)_(2)](ClO_(4))_(2)·0.25H_(2)O(1)和[Cd(2-pyterpy)_(2)]_(2)(ClO_(4))_(4)·2.33H_(2)O·CH_(3)OH(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K_(SV)为2.961×10^(4) 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。

Complexes[Zn(2-pyterpy)_(2)](ClO_(4))_(2)·0.25 H_(2) O(1)and[Cd(2-pyterpy)_(2)]_(2)(ClO_(4))_(4)·2.33 H_(2) O·CH_(3) OH(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.Xray single crystal diffraction results show that they crystallize in the triclinic system with the P1 space group.In solidstate,complexes 1 and 2 showed the maxima emission band approximately at 539 and 547 nm upon excitation at405 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 K_(SV) of 2.961×10^(4) L·mol^(-1),but the fluorescence lifetime of complex1 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.CCDC:2149901,1;2149905,2.