【摘要】 以2,4′-联苯二甲酸(H2bpdc)和1,10-邻菲罗啉(phen)为配体,采用水热法合成一例三维超分子网状镉(Ⅱ)配合物[Cd(bpdc)(phen)2(H2O)]·6H2O(1)。通过单晶X射线衍射分析,元素分析和红外光谱分析表征化合物1的结构。单晶X射线衍射分析结果表明,化合物1属于三斜晶系,P1空间群,中心金属Cd(Ⅱ)离子呈现六配位扭曲八面体构型,通过两种氢键作用和π—π堆积作用形成三维超分子结构。同时,对化合物1进行固态/溶液以及不同温度下的荧光性能测试。以350nm为激发波长进行激发,298K固态时,化合物1在390nm处有强发射峰,呈现紫色荧光;77K固态时,化合物1的荧光光谱具有两个发射谱带,分别位于380和520nm处,是因为在低温时化合物1表现出精细结构。298K时,化合物1在DMSO溶液和CH3OH溶液中分别在380和375nm有最大发射,相对于固态最大发射波长发生蓝移,呈现紫色荧光。这均是基于中心金属微扰配体中心的π*→π跃迁发射。研究了化合物1固态和溶液的荧光寿命,化合物1荧光衰减过程包含双组分。298K条件下,化合物1在DMSO溶液中的寿命(τ1=1.73μs和τ2=14.07μs)比CH3OH溶液中的荧光寿命(τ1=1.21μs和τ2=12.44μs)长。此外,77K固态时的荧光寿命(τ1=1.96μs和τ2=16.11μs)长于298K的固态荧光寿命(τ1=1.20μs和τ2=11.34μs),这是因为低温条件下降低分子内部的非辐射跃迁,从而延长固态荧光寿命。更多还原

【Abstract】 A supramolecular Cd(Ⅱ)complex[Cd(bpdc)(phen)2(H2O)]·6H2O(1)was synthesized with 2,4’-biphenyldicarboxylic acid(H2bpdc)and 1,10-phenanthroline(phen)under hydrothermal conditions and characterized by single-crystal X-ray diffraction elemental analysis,and IR spectrum.Single-crystal X-ray analysis reveals complex 1crystalizes in the triclinic P1 space group,the metal center Cd(Ⅱ)ion is six-coordinated and exhibits a distorted octahedron geometry arrangement.3Dsupramolecular structure could be formed taking into account two kinds of hydrogen bonds andπ—πinteractions.At the same time,we discussed the luminescent properties of complex 1in the solid-state as well as in the solvents at different temperatures.When excited at 350 nm,in the solid state at 298 K,1has purple luminescence with emission band at 390nm;in the solid state at 77 K,1displays two emission bands at 380 and 520nm.Because the vibration structure is more defined at low temperature,at 298 K,1also has purple luminescence in DMSO and CH3 OH solutions with emission bands at 380 and 375nm,which are blue-shifted compared with solid-state maximum emission band.These all can be attribute to theπ*→πtransition based on the coordinate ligands.The fluorescence decay curves of complex 1indicate that the processes of decay consist of two components.At 298 K,the lifetime of 1is longer in DMSO solution(τ1=1.73μs andτ2=14.07μs)than that in CH3 OH solution(τ1=1.21μs andτ2=12.44μs).Moreover,the lifetime of 1is longer at 77K(τ1=1.96μs andτ2= 16.11μs)than that at 298 Kin the solid state(τ1=1.20μs andτ2=11.34μs).The results might be caused by the increase in radiative rate and decrease in non-radiative rate at low temperature.更多还原