Molecular orbital studies of luminescent tetranuclear copper(I) complexes

The electronic structures of the tetranuclear copper(I)complexes [Cu 4(μ-H 2PCH 2PH 2) 4(μ 4-E)] 2+ [E = S(1c), Se(2c)] and [Cu 4(μ-H 2PCH 2PH 2) 4(μ 4-η 1,η 2-C≡C)] 2+ (3c) have been studied using ab initio molecular orbital calculations. It has been found that the high-lying occupied molecular orbitals contain substantial character from the anti-bonding between the Cu(d) orbitals and the ligand orbitals. These molecular orbitals are also mixed with significant Cu(s,p) character. © 1998 Elsevier Science B.V. All rights reserved.link_to_subscribed_fulltex