Synthesis, Crystal Structure and Photoluminescence of a Cuprous Dimer with Tetrakis(pyrazol-i-yl)borate Linker

摘要

A cuprous dimer [Cu(POP)]2(pz4B)BF4·(CH3CN)3(1,POP=bis(2-(diphenylphosphanyl)phenyl)ether,pz4B–=tetrakis(pyrazol-i-yl)borate anion) was synthesized from the reaction of Cu(CH3CN)4BF4,POP and Kpz4 B in CH3 CN at room temperature.The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis.It crystallizes in monoclinic,space group P21/c with a=12.3491(2),b=20.8845(3),c=33.0657(4) ?,β=94.251(1)o,V=8504.3(2) ?3,Z=4,Mr=1693.21,Dc=1.322 g/cm3,F(000)=3496,μ=1.843 mm–1,GOOF=1.031,the final R=0.0442 and w R=0.1235 for 14397 observed reflections with I > 2σ(I).1 is an ionic compound.It is composed of a BF4– anion and a {[Cu(POP)]2(pz4B)}+ cation.The cation contains two [Cu(POP)]+ cationic moieties and a pz4B– anionic linker.The Cu(Ⅰ) ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B– bridging ligand and two phosphorous atoms from a POP terminal chelating ligand.The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature.The Cu(Ⅰ) centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand.The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.