Synthesis, characterization, and photoluminescent studies of three-coordinate Cu(i)–NHC complexes bearing unsymmetrically-substituted dipyridylamine ligands

Abstract

A series of heteroleptic three-coordinate Cu(I) complexes bearing monodentate N-heterocyclic carbene (NHC) ligands of the type 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene (SIPr), and bidentate N-donor ligands of the type unsymmetrically-substituted dimethyl dipyridylamine (Me₂Hdpa) and bis(mesityl)biazanaphthenequinone (mesBIAN) have been synthesized. The complexes [Cu(IPr)(3,4′-Me₂Hdpa)]PF₆, 1; [Cu(IPr)(3,5′-Me₂Hdpa)]PF₆, 2; [Cu(IPr)(3,6′-Me₂Hdpa)]PF₆, 3; [Cu(IPr)(mesBIAN)]PF₆, 6; [Cu(SIPr)(3,4′-Me₂Hdpa)]PF₆, 7; [Cu(SIPr)(3,5′-Me₂Hdpa)]PF₆, 8; and [Cu(SIPr)(3,3′-Me₂Hdpa)]PF₆, 11 have been characterized by ¹H and ¹³C NMR spectroscopies, elemental analysis, cyclic voltammetry, and photophysical studies in solid and solution phase. Single crystal X-ray structures were obtained for all complexes except 11. The crystallographic data reveal a mononuclear structure for all complexes with the copper atom ligated by one C and two N atoms. The UV-Vis absorption spectra of all dipyridylamine complexes in CH₂Cl₂ show a strong ligand-centered absorption band around 250 nm and a strong metal-to-ligand charge transfer (MLCT) band around 300 nm. When irradiated with UV light, the complexes exhibit strong emission maxima at 453–482 nm with photoluminescence quantum yields (PLQY) ranging from 0.21 to 0.87 in solid state. While the PLQY values are comparable to those of the symmetrical [Cu(IPr)(Me₂Hdpa)]PF₆ complexes, a stabilizing CH–π interaction has been reduced in the current systems. In particular, complex 3 lacks any strong CH–π interaction, but emits more efficiently than 1 and 2 wherein the interactions exist. Structural data analysis was performed to clarify the role of ligands' plane angle and the NH/CH⋯F interactions to the observed light interaction of unsymmetrical [Cu(NHC)(Me₂Hdpa)]PF₆ complexes. DFT calculations were performed to assist in the assignment of the electronic structure and excited state behavior of the complexes.