Trialkylphosphine-Stabilized Copper(I) Dialkylaluminum(III) Ethanedithiolate Complexes: Single-Source Precursors and a Novel Modification of Copper Aluminum Disulfide

Abstract

Four types of trialkylphosphine-stabilized copper dialkylaluminum ethanedithiolate complexes with the compositions [(i)Pr3PCuSC2H4SAlR2]2 (R = Me, Et, (i)Pr, (t)Bu, vinyl), [((i)Pr3PCu)3(SC2H4S)2AlR2] (R = Et), [(Me3P)3CuSC2H4SAlR2] (R = Me, Et), and [(Me3P)4Cu][SC2H4SAlR2] (R = Me, Et, (i)Pr) have been synthesized and structurally characterized by X-ray diffraction. The first series features an eight-membered (CuSAlS)2 ring as the core structure. The trimethylphosphine complexes can be distinguished as nonionic and ionic compounds, depending on the amount of trimethylphosphine. In systematic thermogravimetric studies, the complexes were converted into the ternary semiconductor CuAlS2. In this process, a novel wurtzite-type CuAlS2 phase was identified. Binary copper sulfide is observed as a minor side product in thermolysis reactions when volatile trialkylaluminum is released. The thermolysis reactions are completed at temperatures between 330 and 470 °C, depending on the aluminum alkyls. The Cu/Al ratio and phase purity of the thermolysis products were determined by Rietveld analysis of the powder X-ray diffraction patterns and by inductively coupled plasma optical emission spectroscopy measurements. To our knowledge, this is the first study of molecular single-source precursors for CuAlS2.

Festkörperchemie 2014

“…Die Gruppe um Krautscheid verfügt über ein großes Repertoire an multimetallischen Molekülkomplexen und somit über einen Zugang zu metastabilen intermetallischen Phasen. Zum Beispiel führte die Thermolyse eines Kupferdialkylaluminumdithiolat‐Komplexes ([iPr3PCuSC2H4SAlR2]2) zu einem metastabilen Allotrop des Halbleiters CuAlS2 mit Wurtzit‐Struktur 6. Aufgrund der hohen Stabilität der Chalkopyrit‐Struktur ist die Präparation einer neuen Modifikation besonders erwähnenswert (Abbildung 3).…”

Systematic Access of Ternary Organotetrel‐Copper Chalcogenide Clusters by [PhTE3]3− Anions (T=Si, Sn; E=S, Se)

“…[ 18 , 19 , 20 , 21 ] These studies were also expanded to Al compounds like [ i Pr 3 PCuSC 2 H 4 SAlR 2 ] 2 . [ 22 , 23 , 24 ]…”

“…[18][19][20][21] These studies were also expanded to Al compounds like [ i Pr 3 PCuSC 2 H 4 SAlR 2 ] 2 . [22][23][24] While only a few species exist for related compounds including group 15 (semi)metals, [25][26][27] corresponding tin clusters have been explored to a much greater extent. As with the group 13 clusters, tin containing T5-type supertetrahedral anions, e. g., [Cu 2 Ga 16 Sn 2 S 35 ], [28] as well as cages with ligand-free tin atoms, like [Cu 6 Sn 6 S 20 ] 10À , [29][30][31] have been reported.…”

“…Krautscheid and co‐authors have published a series of investigations on compounds exhibiting organic substituents at the group 13 metal, such as [R 3 PCu) 4 (MeM) 4 E 6 ] (R=organic substituent; M=Ga, In) [18–21] . These studies were also expanded to Al compounds like [ i Pr 3 PCuSC 2 H 4 SAlR 2 ] 2 [22–24] …”

Tuning the Properties of the CuAl(1–X)FeXS2 Thin Film as a Potential Absorber for Solar Cell Application

“…In this category, CuAlS 2 came into existence, which has a chalcopyrite tetragonal crystal structure similar to CuInS 2 . In 1955, Hahn and his group first explained the crystal structure of CuAlS 2 in the methodological study of A I B III X 2 (A I = Ag and Cu; B III = Tl, In, Al, and Ga; and X = Te, Se, and S) compounds. , It is a p-type semiconductor with a direct band gap of 3.4 eV, and it is the widest band gap among the chalcopyrite semiconductors . However, the energy band gap is the most vital factor for determining the absorption behavior of a solar cell .…”