A series of soluble trinuclear copper(I) and silver(I) complexes containing bicapped diynyl ligands, [M(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CR)(2)]PF(6) (M = Cu, R = Ph, C(6)H(4)-CH(3)-p, C(6)H(4)-OCH(3)-p, (n)C(6)H(13), H; M = Ag, R = Ph, C(6)H(4)-OCH(3)-p), has been synthesized and their electronic, photophysical, and electrochemical properties studied. The X-ray crystal structures of [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CPh)(2)]PF(6) and [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CH)(2)]PF(6) have been determined.

A series of trinuclear copper(I) thiolate complexes, [Cu(3)(mu-dppm)(3)(mu(3)-SR)(2)]BF(4) (R = C(6)H(4)Cl-4, C(6)H(4)CH(3)-4, C(6)H(4)OCH(3)-4, C(6)H(4)(OCH(3))(2)-3,4, C(6)H(4)-benzo-15-crown-5, or (t)()Bu), [Cu(3)(mu-dppm)(3)(mu(3)-S(t)()Bu)](BF(4))(2), and [Cu(3)(mu-dppm)(3)(mu(3)-SR)(mu(3)-Cl)]BF(4) (R = C(6)H(4)CH(3)-4, C(6)H(4)(t)()Bu-4, or C(6)H(4)(CH(3))(3)-2,4,6) and two hexanuclear copper(I) selenolate complexes, [Cu(6)(mu-P(wedge)P)(4)(mu(3)-SePh)(4)](BF(4))(2) (P(wedge)P = dppm, (Ph(2)P)(2)NH), have been synthesized, and their photophysical properties have been studied. The X-ray crystal structures of both copper(I) selenolate complexes have been determined. These complexes have been shown to exhibit long-lived low-energy emission in solution, attributed to an excited state of predominantly ligand-to-metal charge-transfer [chalcogenolate to copper(I)] origin.