Novel luminescent tetranuclear and pentanuclear copper(I)-dithiolates.

Tetranuclear [Cu(4)mu(2)-dppm)(3)(mu(2)-mu(2)-NS(2))(mu(2)-mu(4)-NS(2))] (1) and pentanuclear [Cu(5)(mu(2)-dppm)(4)(mu(3)-mu-(3)-NS(2))(2)]PF(6) (2.PF(6)) (dppm = bis(diphenylphoshino)methane, NS(2)(2)(-) = 1,8-naphthalenedithiolate) were synthesized from the reactions between NS(2)(2)(-) and [Cu(2)(mu(2)-dppm)(2)(CH(3)CN)(2)](PF(6))(2). Compound 1 features a square Cu(4) core capped by a 5-coordinate S atom while 2.PF(6) exhibits an unprecedented square planar Cu(5) core. Both complexes display dual emissions at 480 and 620 nm which arise from ligand-centered npi and ligand-metal charge-transfer excited states, respectively.