Mononuclear Copper(I) Complexes Containing Redox-active 1,2-Bis(aryl-imino)acenaphthene Acceptor Ligands: Synthesis, Crystal Structures and Tuneable Electronic Properties

A series of pseudo-tetrahedral copper(I) complexes carrying bis(imino)acenaphthene (BIAN) ligands as acceptor subunits and various phosphine derivatives was prepared and characterized by elemental analysis, x-ray crystallography and spectroscopic techniques. The electronic structures of the compounds are dominated by low-lying metal-to-ligand charge transfer (MLCT) transitions which could be systematically modified by different substituent patterns at the diimine acceptor subunit and by variations of the electron donating properties and bite angles of the phosphine moiety. A qualitative concept based on frontier orbital overlap arguments is introduced to describe the observed variations in optical spectra, excited state energies, solvatochromic behaviour, charge transfer character, and extent of electronic coupling following moderate changes in orbital mixing. Due to their readily tuneable properties and the potential of the BIAN ligands to reversibly store up to four redox equivalents, these systems are of considerable interest for the development of novel multielectron transfer photosensitizers which are based on the abundant and environmentally benign transition metal copper.