Synthesis,Structures And Properties Of Copper(I)Clusters

With the rapid development of coordination chemistry,there has been considerable interest in the luminescent properties of transition-metal complexes,particularly in view of their potential applications as sensors and light emitting diodes and in artificial photosynthesis.Ruthenium(II)and Pt(II)complexes with polypyridyl ligands are representative,and have been investigated from various viewpoints.The coinage metal ions with the d10 electron configuration are known to afford emissive complexes.Gold-(I)complexes have been extensively studied because of their strong emission and interesting photophysical properties related to aurophilicity.Copper(I)complexes,which are inexpensive,abundant,and as strongly emissive as d10 Au(I)complexes,have received increased attention.In this paper,the Cu(I)halide(CuI)was used as the starting point,and the conjugated organic ligands with N and S coordination sites were used for molecular self-assembly,and two novel complexes with irreversible thermal transition were successfully synthesized.The photochemical properties of the two complexes were analyzed in detailCu(I)halides and N-containing ligands and S-containing ligands with bridging properties have been extensively studied.In this paper,the bidentate chelate ligand 6,6’-dimethyl-2,2’-Bipyridyl is a premise molecule,which is first reacted with N-Bromosuccinimide to give the intermediate 6,6’-dimethylbromo-2,2’-bipyridyl,then The novel organic ligand 6,6’-bis((benzylthio)methyl)-2,2’-bipyridine(L)(containing N and S bis-coordinating atoms)was obtained by solvothermal reaction with benzyl mercaptan According to the principle of crystallography,two novel complexes with irreversible thermal transition were successfully synthesized.The complexe 2(Cu2I2L)(1)with two rhomboid Cu2I2 core units,exhibits a strong emission peak at 660nm(Xex=460 nm).The complexe Cu4I4L2(2)with step cetane Cu4I4 core unit and exhibits a strong emission peak at 620 nm(Xex=360 nm),which is a classical low-energy emission band with step-cubane Cu4I4 cluster core.