A dinuclear extension to constrained heteroleptic Cu(i) systems

Abstract

This article reports the synthesis and optical properties of three dinuclear, cationic copper complexes [Cu₂(μ-dppm)₂(μ-L)](NO₃)₂ (dppm diphenyldiphosphinomethane, L: L_A 3,6-bis(2-pyridyl)-4,5-diphenyl-pyridazine, L_B 3,6-bis(2-pyridyl)-4,5-di(4-pyridyl)-pyridazine and L_C 3,6-bis(2-pyridyl)-8,9-diazafluoranthene). These were formed on the reaction of [Cu(μ-dppm)(NO₃)]₂ with a series of N-donor (bppn) ligands L. The single crystal X-ray structures of [Cu₂(μ-dppm)₂(μ-L)](NO₃)₂·CH₂Cl₂ were determined and revealed that in both, the two copper atoms are held by three bridging ligands, two dppm ligands and one bppn ligand acting as a tetradentate bridge. The absorption spectra of the complexes present a MLCT [Cu →π*(N^∧N)] band in the λ 370–425 nm region. These new complexes exhibit red-orange MLCT-based emission in the solid-state with lifetimes in the microsecond range. In oxygen-free dichloromethane solution, the complex [Cu₂(μ-dppm)₂(μ-L_C)]²⁺ has a long lifetime of 22.8 μs. The long emission lifetimes are attributed to a rigid conformation that precludes the possible distortion of the copper in the excited state.