两例中性Schiff-base单核Tb(Ⅲ)配合物的合成、结构及荧光性质

Synthesis,structures and fluorescence properties of two mononuclear Tb(Ⅲ)complexes with neutral Schiff base ligands

利用2-羟基-1-萘醛与苯胺衍生物获取中性Schiff配体HL^(1)(1-[N-(4-氯苯基)]氨甲基-2(^(1)H)萘酮)和HL^(2)(1-[N-(4-甲氧基苯基)]氨甲基-2(^(1)H)萘酮),构筑了2例九配位的单核Tb(Ⅲ)配合物[Tb(HL^(1))_(2)(NO_(3))_(3)CH_(3)OH](1Tb,CCDC:2162196)和[Tb(HL^(2))_(3)(NO_(3))_(3)]·CH_(3)CN(2Tb,CCDC:2116221)。通过微调HL配体的末端取代基,配体HL与中心Tb(Ⅲ)离子配位数目从2变为3,同时中心离子的局域对称性也从D_(3h)变为C_(4v)。固体荧光测试发现,1Tb的荧光发射相较于配体出现了红移且荧光强度增加至4倍,2Tb的固态发光强度增长了1倍。此外,2例配合物均表现出低细胞毒性,有望应用于生物传感器或活细胞成像。

Two novel mononuclear 9-coordinate Tb(Ⅲ)complexes,[Tb(HL^(1))_(2)(NO_(3))_(3)CH_(3)OH](1Tb,CCDC:2162196)and[Tb(HL^(2))_(3)(NO_(3))_(3)]·CH_(3)CN(2Tb,CCDC:2116221),had been constructed by neutral Schiff-base ligands HL(1-[N-(4-R)]aminomethyl-2(^(1)H)naphthone,R=-Cl,-OCH_(3))based on 2-hydroxy-1-naphthaldehyde and aniline derivative.By subtle-tuning the terminal substituents of HL ligands,the number of ligands HL coordinated to the central Tb(Ⅲ)ion was changed from 2 to 3,and the local symmetry around Tb(Ⅲ)ion also changed from D_(3h) to C_(4v).Solid-state fluorescence revealed that the emission of 1Tb showed a red shift and the intensity increased to 4 times compared with the ligand HL^(1),while the fluorescence intensity of 2Tb was increased by 1 times.In addition,both complexes exhibited low cytotoxicity and were expected to be used in biosensors or live-cell imaging.