Treatment of [Cu2(dcpm)2]Y2 (dcpm = bis(dicyclohexylphosphino)methane, Y = ClO4-, BF4-, PF6-, CF3SO3-) with refluxing MeOH in the presence of KOH afforded hydride complexes [Cu3(dcpm)3(mu3-H)]Y2 (1) in about 85% yield. Refluxing [Cu2(dcpm)2](PF6)2 with MeOH in the presence of NH3.H2O and air gave a carboxylate complex [Cu2(dcpm)2(O2CCH2OH)]PF6 (2) in 40% yield. All of the complexes 1 and 2 have been characterized by X-ray crystallography. The Cu3 cores in 1 are almost perfectly shielded by the dcpm ligands. Intense photoluminescence was observed for 1 both in the solid state and in solution.

Reactions of MS4(2-) (M = Mo, W) with M'(PCy3)X (M'=Ag/Au, X= ClO4/Cl) and [Cu2(dcpm)2(MeCN)2](ClO4)2 (dcpm = bis(dicyclohexylphosphino)methane) afforded heterometallic sulfido clusters [M'2(PCy3)2(MS4)] (M=Mo, M'=Au: 2; M=W, M'=Ag: 3, Au: 4) and [Cu4(dcpm)4(MS4)](ClO4)2 (M=Mo: 5 x (ClO4)2, W: 6 x (ClO4)2), all of which, except 4, have been characterized by X-ray structure determination. Clusters 5 x(ClO4)2 and 6 x (ClO4)2 feature unusual 16-membered [Cu4P5C4] metallamacrocycles formed on the respective tetrathiometalate anion templates and have unusually long Cu-S bonds and Cu...M distances for metal sulfur clusters that contain a saddle-shaped [Cu4MS4] core. Low-energy absorption bands are observed in their electronic spectra at approximately 562 and 467 nm, respectively, assignable to MMCT transitions; quasireversible reduction waves are observed with E(1/2) = -1.43 (52+) and -1.78 V (62+) versus FeCp2(0/+); and they are emissive either in the solid state or in solution. The emission of 6(2+) can be quenched by both electron acceptors, such as methylviologen, or electron donors, such as aromatic amines, with the excited state reduction potential E(62+*/6+) estimated to be approximately 1.13V versus a normal hydrogen electrode.

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