Unusual effect of carborane ligands on the electronic properties of d0-metal complexes

Abstract

Modern quantum-chemical and photophysical methods have been used to study the structure of the frontier molecular orbitals and the nature of ligand-to-metal charge transfer (LMCT) transitions of structurally complex d⁰-metallocenes. It has been shown that such metal complexes with carboranyl ligands have emissive LMCT states with preferential charge transfer from aromatic π-ligands to the metal and a large electric dipole moment. The electronic excitation and absorption spectra were simulated for the first time, and dipole moments of metal complexes containing metal–carbon σ- and π-bonds were estimated, which is of fundamental importance for the development of molecular photonics.