title: Copper Zinc Thiolate Complexes as Potential Molecular Precursors for Copper Zinc Tin Sulfide (CZTS).
abstract: Five copper zinc thiolate complexes [(iPr3PCu)2(ZnEt2)(edt)]2(1-Et), [(iPr3PCu)2(Zn(iPr)2)(edt)]2(1-iPr), [(iPr3PCu)4(edt)2(ZnMe2)]2(2), [(iPr3PCu)3(ZnPh2)(ZnPh)(edt)2]2(3), and [(iPr3PCu)2Zn2(edt)3]6(4) were prepared by the reaction of [(iPr3PCu)2(edt)]2with ZnR2(R=Me, Et, Ph, iPr) with or without addition of ethanedithiol (edt2-=ethane-1,2-dithiolate). The molecular structures of these complexes were determined by single crystal X-ray diffraction. The ethanedithiolate ligands coordinate in μ3-η1:η2:η1(2, 4), μ4-η1:η1:η2:η1(1-R, 3), and μ5-η1:η1:η2:η1:η1(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-iPr, or 3 with Sn(edt)2were examined by thermogravimetry up to 600 °C, whereupon volatile thermolysis products were identified by mass spectrometry. In all thermolysis experiments, the formation of Cu2ZnSnS4as 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.
authors.affiliation: Universität Leipzig, Institut für Anorganische Chemie, Johannisallee 29, 04103, Leipzig, Germany.
authors.forename: Daniel
authors.initials: D
authors.lastname: Fuhrmann
authors.affiliation: Universität Leipzig, Institut für Anorganische Chemie, Johannisallee 29, 04103, Leipzig, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Dietrich
authors.affiliation: Universität Leipzig, Institut für Anorganische Chemie, Johannisallee 29, 04103, Leipzig, Germany.
authors.forename: Harald
authors.identifier: http://orcid.org/0000-0002-5931-5440
authors.initials: H
authors.lastname: Krautscheid
keywords: Cu2ZnSnS4; X-ray diffraction; copper zinc thiolates; crystal structures; thermolysis