Syntheses, Structures, and Fluxionality of Blue Luminescent Zinc(II) Complexes: Zn(2,2‘,2‘ ‘-tpa)Cl<sub>2</sub>, Zn(2,2‘,2‘ ‘-tpa)<sub>2</sub>(O<sub>2</sub>CCF<sub>3</sub>)<sub>2</sub>, and Zn(2,2‘,3‘ ‘-tpa)<sub>4</sub>(O<sub>2</sub>CCF<sub>3</sub>)<sub>2</sub> (tpa = Tripyridylamine)
作者:Wenyu Yang、Hartmut Schmider、Qingguo Wu、You-sheng Zhang、Suning Wang
DOI:10.1021/ic991436m
日期:2000.5.1
due to a pi *-->pi transition of the tpa ligand as established by an ab initio calculation on the free ligand 2,2',2"-tpa and complex 1. Compounds 1 and 2 are fluxional in solution owing to an exchange process between the coordinate and noncoordinate 2-pyridyl rings of the 2,2',2"-tpa ligand. Compound 2 is also fluxional owing to a cis-trans isomerization process, as determined by variable-temperature
包含2,2',2''-三吡啶胺(2,2',2“ -tpa)或2,2',3”-三吡啶胺(2,2',3“ -tpa)的三种新型Zn(II)络合物已经合成并在结构上表征。化合物1,Zn(2,2',2“ -tpa)Cl2具有四面体几何形状,而化合物2,Zn(2,2',2” -tpa)2(O2CCF3)2和3,Zn(2, 2',3“ -tpa)4(O2CCF3)2具有八面体的几何形状。1和2中的2,2',2” -tpa配体用作双齿配体,与锌中心螯合,而2, 3中的2“,3” -tpa配体用作末端配体,通过3-吡啶基氮原子与锌中心结合。这三种化合物在溶液中和固态时均发出蓝色。溶液中三种化合物的最大发射峰分别为λ= 422、426和432 nm。配合物的蓝色发光归因于tpa配体的pi *-> pi过渡,这是通过对游离配体2,2',2“ -tpa和配合物1的从头算来确定的。由于2,2',2“ -tpa配体