MOLECULAR-ORBITAL STUDIES OF LUMINESCENT TETRANUCLEAR COPPER(I) COMPLEXES

The electronic structures of the tetranuclear copper(I) complexes [Cu- 4(mu-H2PCH2PH2)(4)(mu(4)-E)](2+) [E = S(1c), Se(2c)] and [Cu-4(mu-H2PC H2PH (2))(4)(mu(4)-eta(1),eta(2)-C=C)](2+) (3C) have been studied usin g 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 orbita ls. These molecular orbitals are also mixed with significant Cu(s,p) c haracter. (C) 1998 Elsevier Science B.V. All rights reserved.