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1,2‐Dithiooxalato‐Bridged Heterobimetallic Complexes as Single‐Source Precursors for Ternary Metal Sulfide Semiconductors
Author(s) -
Nowotny Mathias,
Foro Sabine,
Heinschke Silvio,
Hoffmann Rudolf C.,
Schneider Jörg J.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402990
Subject(s) - chemistry , bimetallic strip , ternary operation , metal , chalcogenide , oleylamine , crystallography , thermal decomposition , thermal stability , inorganic chemistry , nanotechnology , nanocrystal , organic chemistry , materials science , computer science , programming language
The new 1,2‐dithiooxalato‐bridged bimetallic Cu–Ga, Cu–In, and Cu–Sn complexes [{(Ph 3 P) 2 Cu(μ‐S 2 C 2 O 2 )} 3 Ga] ( 1 ), [{(Ph 3 P) 2 Cu(μ‐S 2 C 2 O 2 )} 3 In] ( 2 ), [(Ph 3 P) 2 Cu(μ‐S 2 C 2 O 2 )In(S 2 CNEt 2 ) 2 ] ( 3 ), and [{(Ph 3 P) 2 Cu(μ‐S 2 C 2 O 2 )} 2 Sn(S 2 C 2 O 2 )] ( 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 CuInS 2 and Cu 2 SnS 3 , 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 CuInS 2 (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 Sn II and Sn IV intermediates in the case of SSP [{(Ph 3 P) 2 Cu(μ‐S 2 C 2 O 2 )} 2 Sn(S 2 C 2 O 2 )] ( 4 ).