柔性双咪唑配体环状金(Ⅰ)配合物的合成、表征及荧光性质

Synthesis,Characterization and Fluorescence Properties of Macrocyclic Gold(Ⅰ) Complexes with Flexible Bisimidazolate-Containing Ligands

采用扩散法制备了2个基于柔性双咪唑配体的Au(Ⅰ)配合物,[Au2(m-bitmb)2][AuCl2]Cl·2CH3OH(1)和[Au2(m-bitmb)2][AuCl2]2·2CH3CN(2)(m-bitmb=1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene),并使用X射线单晶衍射、元素分析、XRD等测试手段进行了表征,研究了配合物的荧光性质。结构分析结果表明配合物1和2均具有M2L2的环状结构单元,其结构中双齿配体m-bitmb均采用顺式构型参与配位,M2L2结构单元通过π-π堆积相互作用排列而形成一维链状结构。配合物1和2具有更强的π-π堆积作用,但亲金性稍弱。通过对比2种配合物和配体的荧光发射,发现配合物中存在的亲金相互作用对其荧光性质具有很重要的影响和作用。

Two novel cyclic Au(Ⅰ)complexes based on flexible bisimidazole-containing ligand,namely,[Au2(m-bitmb)2][AuCl2]Cl·2CH3OH(1)and[Au2(m-bitmb)2][AuCl2]2·2CH3CN(2)(m-bitmb=1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene),respectively,were obtained by diffusion method,which were further characterized by X-ray single crystal diffraction,elemental analysis,XRD and fluorescence spectroscopy.Complex 1 crystallizes in space group P2/c with a=0.8956(9)nm,b=1.1290(12)nm,c=2.1663(2)nm,β=91.934(19)°,V=2.1821(4)nm3,Z=2,Dc=2.012 g·cm-3,F(000)=1248,the final R=0.0366,wR=0.0910.Complex 2 crystallizes in space group P1 with a=0.84716(13)nm,b=1.16882(17)nm,c=1.18372(17)nm,α=97.1320(10)°,β=96.872(2)°,γ=95.391(2)°,V=1.1476(3)nm3,Z=1,Dc=2.275 g·cm^-3,F(000)=728,the final R=0.0381,wR=0.0878.Both the title complexes have similar cyclic M2L2 structural units.The m-bitmb in 1 and 2 all adopt cis-conformation to coordinate to Au(Ⅰ)centers.The cyclic units in 1 and 2 are regularly arranged throughπ-πstacking interaction to form one-dimensional chain structures.Complex 1 has strongerπ-πstacking effect than 2,but its aurophility is slightly weaker.The structural diversities of title complexes may be caused by the different solvents used in the synthesis process.Fluorescence results show that the aurophilic interactions in title complexes play important roles on their fluorescence properties.CCDC:1942464,1;1942465,2.