Copper(I) tert-butylthiolato clusters as single-source precursors for high-quality chalcocite thin films: Precursor chemistry in solution and the solid state

Sven Schneider; Alma Dzudza; Gabriele Raudaschl-Sieber; Tobin J. Marks

doi:10.1021/cm0700504

Copper(I) tert-butylthiolato clusters as single-source precursors for high-quality chalcocite thin films: Precursor chemistry in solution and the solid state

Sven Schneider, Alma Dzudza, Gabriele Raudaschl-Sieber, Tobin J. Marks

Northwestern University

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

Polymeric (CuS^tBu)_∞ (1) undergoes reaction with trialkylphosphines to form the cuprous thiolato phosphine complexes [(CuS ^tBu)₄(PR₃)₂] (R = Me (2a), Et (2b)) in high yield. In contrast to 2b, in polar solvents (CH₂Cl ₂, tetrahydrofuran), complex 2a is in equilibrium with the ion pair Cu(PMe₃)₄⁺Cu₅(S^tBu) ₆^- (3) and other species such as (CuS^tBu) _x(PMe₃)₂ (x = 6 (4), 8 (5)). Clusters 2-4 were isolated analytically pure and fully characterized in solution by multinuclear nuclear magnetic resonance (NMR) spectroscopy and in the solid state by single-crystal X-ray diffraction and ³¹P magic angle spinning NMR spectroscopy, while the structure of compound 5 was determined by single-crystal X-ray diffraction. Thermal analysis (TGA/DTA) and examination of the volatile byproducts suggest stepwise phosphine loss and C-S bond cleavage by isobutene elimination as the predominant thermolysis pathways of this new Cu₂S precursor class.

Original language	English
Pages (from-to)	2768-2779
Number of pages	12
Journal	Chemistry of Materials
Volume	19
Issue number	11
DOIs	https://doi.org/10.1021/cm0700504
Publication status	Published - May 29 2007

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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Copper(I) tert-butylthiolato clusters as single-source precursors for high-quality chalcocite thin films : Precursor chemistry in solution and the solid state. / Schneider, Sven; Dzudza, Alma; Raudaschl-Sieber, Gabriele; Marks, Tobin J.

In: Chemistry of Materials, Vol. 19, No. 11, 29.05.2007, p. 2768-2779.

Research output: Contribution to journal › Article › peer-review

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abstract = "Polymeric (CuStBu)∞ (1) undergoes reaction with trialkylphosphines to form the cuprous thiolato phosphine complexes [(CuS tBu)4(PR3)2] (R = Me (2a), Et (2b)) in high yield. In contrast to 2b, in polar solvents (CH2Cl 2, tetrahydrofuran), complex 2a is in equilibrium with the ion pair Cu(PMe3)4+Cu5(StBu) 6- (3) and other species such as (CuStBu) x(PMe3)2 (x = 6 (4), 8 (5)). Clusters 2-4 were isolated analytically pure and fully characterized in solution by multinuclear nuclear magnetic resonance (NMR) spectroscopy and in the solid state by single-crystal X-ray diffraction and 31P magic angle spinning NMR spectroscopy, while the structure of compound 5 was determined by single-crystal X-ray diffraction. Thermal analysis (TGA/DTA) and examination of the volatile byproducts suggest stepwise phosphine loss and C-S bond cleavage by isobutene elimination as the predominant thermolysis pathways of this new Cu2S precursor class.",

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