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^*

^*Corresponding author for this work

Chemistry

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

19 Scopus citations

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 (US)
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
State	Published - May 29 2007

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/cm0700504

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

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.",

author = "Sven Schneider and Alma Dzudza and Gabriele Raudaschl-Sieber and Marks, {Tobin J.}",

year = "2007",

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doi = "10.1021/cm0700504",

language = "English (US)",

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T1 - Copper(I) tert-butylthiolato clusters as single-source precursors for high-quality chalcocite thin films

T2 - Precursor chemistry in solution and the solid state

AU - Schneider, Sven

AU - Dzudza, Alma

AU - Raudaschl-Sieber, Gabriele

AU - Marks, Tobin J.

PY - 2007/5/29

Y1 - 2007/5/29

N2 - 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.

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

Abstract

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CCDC 658368: Experimental Crystal Structure Determination

CCDC 658369: Experimental Crystal Structure Determination

CCDC 658366: Experimental Crystal Structure Determination

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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

Abstract

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Datasets

CCDC 658368: Experimental Crystal Structure Determination

CCDC 658369: Experimental Crystal Structure Determination

CCDC 658366: Experimental Crystal Structure Determination

Cite this