1,2‐Dithiooxalato‐Bridged Heterobimetallic Complexes as Single‐Source Precursors for Ternary Metal Sulfide Semiconductors

Abstract

AbstractThe new 1,2‐dithiooxalato‐bridged bimetallic Cu–Ga, Cu–In, and Cu–Sn complexes [{(Ph3P)2Cu(μ‐S2C2O2)}3Ga] (1), [{(Ph3P)2Cu(μ‐S2C2O2)}3In] (2), [(Ph3P)2Cu(μ‐S2C2O2)In(S2CNEt2)2] (3), and [{(Ph3P)2Cu(μ‐S2C2O2)}2Sn(S2C2O2)] (4) were prepared and spectroscopically fully characterized. The crystal structures of 2–4 are presented. Complexes 3 and 4 are potential molecular single‐source precursors (SSP) for the ternary semiconductors CuInS2 and Cu2SnS3, respectively, which can be manipulated under ambient conditions. Indeed, a study of the thermal degradation of 3 and 4 revealed that 3 affords pure nanoscaled CuInS2 (mean diameter ca. 2 nm) when the decomposition is carried out in an oleylamine solution by using a hot‐injection or arrested‐precipitation technique at temperatures well below 250 °C. In contrast, 4 decomposes under the same reaction conditions in an ambiguous manner and forms mixed binary chalcogenide phases. This can be explained by a subtle influence of the relative stability of possible SnII and SnIV intermediates in the case of SSP [{(Ph3P)2Cu(μ‐S2C2O2)}2Sn(S2C2O2)] (4).