铽-磺酰基杯[4]芳烃单核配合物的单晶结构转变和发光性质

Structural Transformation and Luminescence Properties of Terbium-sulfonylcalix[4]arene Mononuclear Complexes

由对叔丁基-磺酰基杯[4]芳烃(H_(4)TC4A-SO_(2))和Tb(CH_(3)COO)_(3)制备了一例单核铽-杯芳烃配位化合物(Tb_(1)-A).杯芳烃能够敏化铽离子,使Tb_(1)-A无论固体状态还是在甲醇溶液中均能有效发光.通过荧光滴定发现,1,10-菲啰啉(phen)与Tb_(1)-A存在两种明显不同的作用模式,并可影响其发光性能.通过单晶结构分析表征了滴定过程中的两个单核化合物(Tb_(1)-B和Tb_(1)-C),确定了phen与Tb_(1)-A两种不同的作用模式,其中一种作用模式是phen与稀土离子的配位作用,另一种作用模式是phen与杯芳烃的主-客体相互作用.两种作用模式对稀土发光的影响不同.结合理论计算结果发现,客体分子与杯芳烃间的主-客体相互作用是导致荧光变化的主要因素.

A mononuclear terbium coordination compound(Tb_(1)-A)was prepared from t-tert-butyl-sulfonylcalixarene(H_(4)TC4A-SO_(2))and Tb(CH_(3)COO)_(3).Calixarene can effectively sensitize terbium ions,enabling luminescence of Tb_(1)-A in both solid state and methanol solution.It was found that 1,10-phenanthroline(phen)could influence the luminescence of Tb_(1)-A by two interaction modes in fluorescence titration.Two different contacting modes between phen and Tb_(1)-A were also determined by the single crystal structural characterization of two mononuclear compounds(Tb_(1)-B and Tb_(1)-C),one of which was the coordination between phen and Tb ions,the other was the host-guest inter-action between phen and calixarene.Combined with the results of theoretical calculation,it was also found that the host-guest interaction between guest molecules and calixarene was the main factor that caused the fluorescence quenching.