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

Novel heterobimetallic complexes [(PPh3)2Cu(μ-SCOPh)2Cd(SCOPh)] (2a), [(PPh3)2Cu(μ-SCOth)2Cd(SCOth)] (2b), [(PPh3)2Ag(μ-SCOth)2Cd(SCOth)] (3a), [(PPh3)2Ag(μ-SCOth)2Cd(H2O)(SCOth)] (3b), [(PPh3)2Ag(μ-SCOPh)2Cd(SCOPh)] (3c), and a bimetallic complex [PPh3Cd(μ-SCOth)SCOth]2·CH2Cl2 (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 CuCd7S8, CuCd10S11, Ag2Cd8S9, and Ag2Cd5S6, which have been characterized by SEM-EDX and X-ray diffractometry. Photophysical properties and electrical conductivities of the sulfides have also been studied.

本研究合成了一系列新型异双金属配合物：[(三苯基膦(triphenylphosphine, PPh₃))₂Cu(μ-SCOPh)₂Cd(SCOPh)] (2a)、[(三苯基膦(triphenylphosphine, PPh₃))₂Cu(μ-SCOth)₂Cd(SCOth)] (2b)、[(三苯基膦(triphenylphosphine, PPh₃))₂Ag(μ-SCOth)₂Cd(SCOth)] (3a)、[(三苯基膦(triphenylphosphine, PPh₃))₂Ag(μ-SCOth)₂Cd(H₂O)(SCOth)] (3b)、[(三苯基膦(triphenylphosphine, PPh₃))₂Ag(μ-SCOPh)₂Cd(SCOPh)] (3c)，以及双金属配合物[(三苯基膦(triphenylphosphine, PPh₃))Cd(μ-SCOth)SCOth]₂·CH₂Cl₂ (5)（其中th代表噻吩(thiophene)），并通过单晶X射线衍射分析对上述配合物完成了结构表征。此外，本研究还对配位聚合物[Cd(SCOPh)₂]ₙ (4) 进行了结构表征，该聚合物展现出类金属导电性。将上述异双金属配合物在受控条件下进行热解，可得到组成为CuCd₇S₈、CuCd₁₀S₁₁、Ag₂Cd₈S₉及Ag₂Cd₅S₆的三元硫化物，并通过扫描电子显微镜-能量色散X射线光谱(SEM-EDX)与X射线衍射法对其进行了表征。此外，本研究还对上述三元硫化物的光物理性质与导电性能开展了相关研究。