The Chemistry of Cadmium–Thiocarboxylate Derivatives: Synthesis, Structural Features, and Application As Single Source Precursors for Ternary Sulfides

Abstract

Novel heterobimetallic complexes [(PPh(3))(2)Cu(μ-SCOPh)(2)Cd(SCOPh)] (2a), [(PPh(3))(2)Cu(μ-SCOth)(2)Cd(SCOth)] (2b), [(PPh(3))(2)Ag(μ-SCOth)(2)Cd(SCOth)] (3a), [(PPh(3))(2)Ag(μ-SCOth)(2)Cd(H(2)O)(SCOth)] (3b), [(PPh(3))(2)Ag(μ-SCOPh)(2)Cd(SCOPh)] (3c), and a bimetallic complex [PPh(3)Cd(μ-SCOth)SCOth](2)·CH(2)Cl(2) (5) (th = thiophene) were prepared and characterized by single crystal X-ray diffraction analysis. A coordination polymer [Cd(SCOPh)(2)](n) (4) has also been characterized structurally that exhibited metal-like electrical conductivity. The heterobimetallic complexes on pyrolyzing under controlled conditions yielded ternary sulfides of composition CuCd(7)S(8), CuCd(10)S(11), Ag(2)Cd(8)S(9), and Ag(2)Cd(5)S(6), which have been characterized by SEM-EDX and X-ray diffractometry. Photophysical properties and electrical conductivities of the sulfides have also been studied.

A semiconducting microporous framework of Cd6Ag4(SPh)16 clusters interlinked using rigid and conjugated bipyridines

“…Selective control of the decomposition might allow cluster 1 to produce a ternary Cd x Ag 2À2x S compound. 22 Further study of the decomposition of clusters such as 1 might yield new means to prepare hybrid or ternary semiconductors.…”

Syntheses and structural studies of heterobimetallic thiocarboxylate complexes containing zinc and silver

“…In general, lower energy peaks appear because of the metal to ligand (or ligand to metal) charge transfers while peaks below 300 nm are due to the inter-or intra-ligand charge transfers. Spectral behavior of both the complexes are very similar to the thiocarboxylate complexes of Cd(II)/Ag(I) [15] and Pb(II)/Ag(I) [17].…”

“…Apart from the tuned properties such heterobimetallic systems are extremely useful as precursors of electronic materials [10][11][12][13]. During recent years, heterobimetallic complexes containing sulfur donor ligands are being utilized to prepare ternary metal sulfides by soft chemical routes which are more energy efficient as compared to conventional sintering methods [14,15]. Some times back we had reported [16] the synthesis and structure of the complex anion [In(SCOPh) 4 ] À which has been used to prepare a number of heterobimetallic complexes useful as single source precursors of binary and ternary metal sulfides [14].…”

Studies of synthesis, structural features of Cu(i) thiophene-2-thiocarboxylates and unprecedented desulfurization of Cu(ii) thiocarboxylate complexes

“…In addition, a homoleptic Cu(I) complex [Cu(SC{O}Me) 2 ]has also been reported. 8 A few heterobimetallic thiocarboxylate complexes containing Cu(I)/In(III), 9 Cu(I)/Pb(II), 10 Cu(I)/Zn(II) and Cu(I)/Cd(II) 11 have also been synthesized and characterized structurally. Notably, in all these complexes, the thiocarboxylate ligand is bound essentially through the sulfur atom (though oxygen atom in some cases is also bound to the metal).…”