Molecular orbital studies of luminescent silver(I) chalcogenido clusters [Ag4(μ-dppm)4(μ4-E)]2+ (dppm = Ph2PCH2PPh2)

The electronic structures of the μ4-chalcogenido silver(I) complexes [Ag4(μ-dppm)4(μ4-E)] [O3SCF3]2 (E = S 1, Se 2 or Te 3; dppm = Ph2PCH2PPh2) have been calculated by use of the Fenske-Hall molecular orbital method. The results indicate that complexes 1-3 show similar electronic structures, with the highest occupied molecular orbital being mainly of Ag-E character while the lowest unoccupied molecular orbital is of metal-metal interaction character. A correlation between the results of these calculations with the spectroscopic properties of this class of complexes is described.link_to_subscribed_fulltex