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Copper Zinc Thiolate Complexes as Potential Molecular Precursors for Copper Zinc Tin Sulfide (CZTS)
Author(s) -
Fuhrmann Daniel,
Dietrich Stefan,
Krautscheid Harald
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604717
Subject(s) - zinc , chemistry , copper , metal , thermal decomposition , crystallography , tin , powder diffraction , crystal structure , inorganic chemistry , thermogravimetry , nuclear chemistry , organic chemistry
Five copper zinc thiolate complexes [( i Pr 3 PCu) 2 (ZnEt 2 )(edt)] 2 ( 1‐Et ), [( i Pr 3 PCu) 2 (Zn( i Pr) 2 )(edt)] 2 ( 1‐ i Pr ), [( i Pr 3 PCu) 4 (edt) 2 (ZnMe 2 )] 2 ( 2 ), [( i Pr 3 PCu) 3 (ZnPh 2 )(ZnPh)(edt) 2 ] 2 ( 3 ), and [( i Pr 3 PCu) 2 Zn 2 (edt) 3 ] 6 ( 4 ) were prepared by the reaction of [( i Pr 3 PCu) 2 (edt)] 2 with ZnR 2 (R=Me, Et, Ph, i Pr) with or without addition of ethanedithiol (edt 2− =ethane‐1,2‐dithiolate). The molecular structures of these complexes were determined by single crystal X‐ray diffraction. The ethanedithiolate ligands coordinate in μ 3 –η 1 :η 2 :η 1 ( 2 , 4 ), μ 4 –η 1 :η 1 :η 2 :η 1 ( 1‐R , 3 ), and μ 5 –η 1 :η 1 :η 2 :η 1 :η 1 ( 2 ) bridging modes, each sulfur atom binds to two or three metal atoms. Evidence for the presence of the weak Zn−S bonds in solution was provided by NMR spectroscopy. Mixtures of 1‐Et , 1‐ i Pr , or 3 with Sn(edt) 2 were examined by thermogravimetry up to 600 °C, whereupon volatile thermolysis products were identified by mass spectrometry. In all thermolysis experiments, the formation of Cu 2 ZnSnS 4 as main product, besides small amounts of binary metal sulfides, was confirmed by X‐ray powder diffraction (PXRD) and EDX (energy dispersive X‐ray spectroscopy) analysis.