Copper Zinc Thiolate Complexes as Potential Molecular Precursors for Copper Zinc Tin Sulfide (CZTS)

Abstract

Five copper zinc thiolate complexes [(iPr PCu) (ZnEt )(edt)] (1-Et), [(iPr PCu) (Zn(iPr) )(edt)] (1-iPr), [(iPr PCu) (edt) (ZnMe )] (2), [(iPr PCu) (ZnPh )(ZnPh)(edt) ] (3), and [(iPr PCu) Zn (edt) ] (4) were prepared by the reaction of [(iPr PCu) (edt)] with ZnR (R=Me, Et, Ph, iPr) with or without addition of ethanedithiol (edt =ethane-1,2-dithiolate). The molecular structures of these complexes were determined by single crystal X-ray diffraction. The ethanedithiolate ligands coordinate in μ -η :η :η (2, 4), μ -η :η :η :η (1-R, 3), and μ -η :η :η :η :η (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) 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 ZnSnS 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.

Ternary Mixed‐Valence Organotin Copper Selenide Clusters

“…The family of discrete metal chalcogenide clusters with aternary inorganic core comprises ad iversity of structural motifs and compositions, ranging from ligand-stabilized neutral heterocubanes [1][2][3][4] to huge anionic supertetrahedra, [5][6][7] and from clusters of moderate size [8] to compounds on an anometer scale. [9,10] These feature combinations of different transition metal atoms [11][12][13][14] or different main group metal atoms, [15] or both, [16][17][18][19] or they combinea toms of transition metals and lanthanides. [20][21][22] Our work aims to combine Group 14 atoms (T = Ge, Sn, Pb) with transition metal atoms Mi nt ernary chalcogenide-bridged clusters (E = S, Se, Te )f or fine-tuning of their structural and optoelectronic properties.…”

“…The family of discrete metal chalcogenide clusters with a ternary inorganic core comprises a diversity of structural motifs and compositions, ranging from ligand‐stabilized neutral heterocubanes to huge anionic supertetrahedra, and from clusters of moderate size to compounds on a nanometer scale . These feature combinations of different transition metal atoms or different main group metal atoms, or both, or they combine atoms of transition metals and lanthanides …”

Homoleptic Group 13 Trimethylsilylchalcogenolato Metalates [M(ESiMe3)4]− (M = Ga, In; E = S, Se): Metastable Precursors for Low-Temperature Syntheses of Chalcogenide-Based Materials

“…Note that the low solubility of 1 in THF led to very weak signals in the 13 C NMR spectra, preventing the observation of coupling of 13 C with 15 N, and a vanishingly low visibility of the signal at 66. 4 Synthesis of DMPyr[Ga(SeSiMe 3 ) 4 ] (2). With continuous stirring at 0 °C n-BuLi (2.9 M, 0.27 mL, 0.77 mmol, 3.0 equiv) was added dropwise to a solution of Se(SiMe 3 ) 2 (180 mg, 0.80 mmol, 3.1 equiv) in thf (10 mL).…”

“…The mixture was filtered off from the crude product, and the filtrate was stored at −30 °C for 24 h to obtain colorless crystals. The mother 4 J CP = 3.0 Hz, P(C(CHCH) 2 (CH)) 4 ), 135.5 (d, 3 J CP = 10.7 Hz, P(C(CHCH) 2 (CH)) 4 ), 131.3 (d, 2 J CP = 13.0 Hz, P(C(CHCH) 2 (CH)) 4 ), 118.9 (d, 1 J C P = 89.2 Hz, P-(C(CHCH) 2 (CH)) 4 ), 6.0 (s, [In(SSi(CH 3 ) 3 ) 4 ] − ) ppm. 29 ].…”

Synthesis and Crystal Structures of Copper Zinc Phenylthiolate and the First Copper Zinc Selenolate and Tellurolate Complexes

“…However, to the best of our knowledge no Cu‐Zn‐Se and Cu‐Zn‐Te complexes have been published so far. We recently reported on synthesis, structural characterization, and thermolysis studies of a series of heteronuclear copper zinc ethandithiolate complexes . Herein we present the synthesis and characterization of novel copper zinc phenylchalcogenolate complexes including the first selenolate and tellurolate complexes of this type.…”