Structural and Photophysical Studies of Phosphorescent Three-Coordinate Copper(I) Complexes Supported by an N-Heterocyclic Carbene Ligand

A series of four neutral luminescent three-coordinate Cu(I) complexes (IPr)Cu(N boolean AND N), where IPr is a monodentate N-heterocyclic carbene (NHC) ligand (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) and N boolean AND N denotes monoanionic pyridyl-azolate ligands, have been synthesized and characterized. A monomeric, three-coordinate geometry, best described as distorted trigonal planar, has been established by single-crystal X-ray analyses for three of the derivatives. In contrast to the previously reported (IPr)Cu(N boolean AND N) complexes, the compounds described here display a perpendicular orientation between the chelating N boolean AND N ligands and the imidazolylidene ring of the carbene ligand. The geometrical preferences revealed by X-ray crystallography correlate well with the NMR data. The conformational behavior of the complexes, investigated by variable-temperature H-1 NMR spectroscopy, indicate free rotation about the C-NHC-Cu bond in solution the complexes display broad, featureless luminescence at both room temperature and 77 K, with emission maxima that vary between 555 and 632 nm depending on sample Conditions. Luminescence quantum efficiencies of the complexes in solution (Phi <= 17%) increase markedly in the solid state (Phi <= 62%). On the basis, of time dependent density functional theory (TD-DFT) calculations and the. experimental data, luminescence is assigned to phosphorescence from a metal-to-ligand charge transfer (MLCT) triplet state admixed with ligand-centered (LC) character.