A novel triply bridged dinuclear four-coordinate copper(I) complex with sterically bulky bis(dicyclohexylphosphino)methane ligand

作者：Yao, Zu Fu^*; Gan, Xin; Fu, Wen Fu

来源：Central European Journal of Chemistry, 2008, 6(4): 613-616.

DOI：10.2478/s11532-008-0057-9

• Copper(I) complex
• Dcpm ligand
• Paa ligand
• Crystal structure
• Photophysical properties

A novel triply bridged dinuclear copper(I) complex: Cu-2(mu-paa)(mu-dcpm)(2)(BF4)(2)center dot 2CH(2)Cl(2) [ paa = pyridine-2-carbaldehyde azine (C12H10N4) and dcpm = bis(dicyclohexylphosphino)methane(C25H46P2) ] has been synthesized and structurally characterized. Crystallographic studies of the complex showed that two copper(I) ions were bridged by one paa ligand and two dcpm ligands. The paa ligand adopted the Z configuration at the partially double N-N bond and the two copper ions have distorted tetrahedral coordination geometry. Because of the steric effect of dcpm, the pyridine rings of the paa ligand are obviously not on the same plane (the dihedral angle is 43.61(0)). The interaction between neighboring ligands results in a N-N bond length (1.374(7) angstrom) contraction. The UV-vis spectra of the complex exhibited intense high-energy absorptions at lambda(max) < 340 nm and broad visible bands in a range of 380-550 nm, ascribed to intraligand (IL pi-pi*) transitions and metal-to-ligand charge-transfer (MLCT) transitions, respectively. Interestingly, the absorbtion peaks varied regularly with the solvent polarity. Although the complex has a rigid structure with the copper ions held firmly by triply bridged ligands, the emission and excitation spectra revealed that the complex exhibits weak fluorescence.

• 出版日期2008-12
• 单位云南师范大学; 中国科学院理化技术研究所; 湖南医药学院