Trialkylphosphine-Stabilized Copper(I) Gallium(III) Phenylchalcogenolate Complexes: Crystal Structures and Generation of Ternary Semiconductors by Thermolysis

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R3P)mCunMe2–xGa­(EPh)n+x+1] (R = Me, Et, iPr, tBu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga–E bonds are relatively rigid, in contrast to flexible Cu–E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga–E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga–E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE2. The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me3Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors

Trialkylphosphine-Stabilized Copper(I) Gallium(III) Phenylchalcogenolate Complexes: Crystal Structures and Generation of Ternary Semiconductors by Thermolysis

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R₃P)<i>_m</i>Cu<i>_n</i>Me_2–<i>x</i>Ga­(EPh)_{<i>n</i>+<i>x</i>+1}] (R = Me, Et, ⁱPr, ^tBu; E = S, Se, Te; <i>x</i> = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga–E bonds are relatively rigid, in contrast to flexible Cu–E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga–E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga–E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE₂. The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me₃Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors

Hydrothermal Synthesis and Structure of Coordination Polymers by Combination of Bipyrazole and Aromatic Dicarboxylate Ligands

Nine new coordination polymers, namely 2∞[Ag(Hp2CA)(Me4bpz)] (I), 3∞[Zn2(p2CA)2(Me4bpz)] (II), 2∞[Cd(OAc)2(Me4bpz)(H2O)] (III), 1∞[Ag2(m2CA)(Me4bpz)2] (IV), 3∞[Zn(m2CA)(Me4bpz)] (V), 2∞[Cd(m2CA)(Me4bpz)]·H2O (VI), 1∞[Ag(OAc)(Me4bpz)2]·5.4 H2O (VII), 3∞[Zn2(OHm2CA)2(Me4bpz)2]·1.75 H2O (VIII), and 2∞[Cd(OHm2CA)(Me4bpz)(H2O)] (IX) [Hp2CA, terephthalic acid monoanion; p2CA, terephthalic acid dianion; OAc, acetate; m2CA, isophthalic acid dianion; OHm2CA, 5-hydroxy-isophthalic acid dianion; Me4bpz, 3,3′,5,5′-tetramethyl-4,4′-bipyrazole], were obtained from acetate hydrates of Ag+, Zn2+, and Cd2+ and mixed ligand systems consisting of Me4bpz and the respective aromatic dicarboxylic acid by means of hydrothermal synthesis. The compounds were characterized by means of X-ray single-crystal structure analysis, elemental analysis, and IR spectroscopy. The topologies realized in these coordination polymers vary from simple one-dimensional polymers to complex three-dimensional frameworks. Hydrogen bonds of different types with influence on the resulting structures are observed in all compounds

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

Four types of trialkylphosphine-stabilized copper dialkylaluminum ethanedithiolate complexes with the compositions [iPr3PCuSC2H4SAlR2]2 (R = Me, Et, iPr, tBu, vinyl), [(iPr3PCu)3(SC2H4S)2AlR2] (R = Et), [(Me3P)3CuSC2H4SAlR2] (R = Me, Et), and [(Me3P)4Cu]­[SC2H4SAlR2] (R = Me, Et, iPr) 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

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

Four types of trialkylphosphine-stabilized copper dialkylaluminum ethanedithiolate complexes with the compositions [^<i>i</i>Pr₃PCuSC₂H₄SAlR₂]₂ (R = Me, Et, ^<i>i</i>Pr, ^<i>t</i>Bu, vinyl), [(^<i>i</i>Pr₃PCu)₃(SC₂H₄S)₂AlR₂] (R = Et), [(Me₃P)₃CuSC₂H₄SAlR₂] (R = Me, Et), and [(Me₃P)₄Cu]­[SC₂H₄SAlR₂] (R = Me, Et, ^<i>i</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

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

Four types of trialkylphosphine-stabilized copper dialkylaluminum ethanedithiolate complexes with the compositions [^<i>i</i>Pr₃PCuSC₂H₄SAlR₂]₂ (R = Me, Et, ^<i>i</i>Pr, ^<i>t</i>Bu, vinyl), [(^<i>i</i>Pr₃PCu)₃(SC₂H₄S)₂AlR₂] (R = Et), [(Me₃P)₃CuSC₂H₄SAlR₂] (R = Me, Et), and [(Me₃P)₄Cu]­[SC₂H₄SAlR₂] (R = Me, Et, ^<i>i</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

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

Four types of trialkylphosphine-stabilized copper dialkylaluminum ethanedithiolate complexes with the compositions [iPr3PCuSC2H4SAlR2]2 (R = Me, Et, iPr, tBu, vinyl), [(iPr3PCu)3(SC2H4S)2AlR2] (R = Et), [(Me3P)3CuSC2H4SAlR2] (R = Me, Et), and [(Me3P)4Cu]­[SC2H4SAlR2] (R = Me, Et, iPr) 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

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

Four types of trialkylphosphine-stabilized copper dialkylaluminum ethanedithiolate complexes with the compositions [iPr3PCuSC2H4SAlR2]2 (R = Me, Et, iPr, tBu, vinyl), [(iPr3PCu)3(SC2H4S)2AlR2] (R = Et), [(Me3P)3CuSC2H4SAlR2] (R = Me, Et), and [(Me3P)4Cu]­[SC2H4SAlR2] (R = Me, Et, iPr) 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

Hydrothermal Synthesis and Structure of Coordination Polymers by Combination of Bipyrazole and Aromatic Dicarboxylate Ligands

Nine new coordination polymers, namely 2∞[Ag(Hp2CA)(Me4bpz)] (I), 3∞[Zn2(p2CA)2(Me4bpz)] (II), 2∞[Cd(OAc)2(Me4bpz)(H2O)] (III), 1∞[Ag2(m2CA)(Me4bpz)2] (IV), 3∞[Zn(m2CA)(Me4bpz)] (V), 2∞[Cd(m2CA)(Me4bpz)]·H2O (VI), 1∞[Ag(OAc)(Me4bpz)2]·5.4 H2O (VII), 3∞[Zn2(OHm2CA)2(Me4bpz)2]·1.75 H2O (VIII), and 2∞[Cd(OHm2CA)(Me4bpz)(H2O)] (IX) [Hp2CA, terephthalic acid monoanion; p2CA, terephthalic acid dianion; OAc, acetate; m2CA, isophthalic acid dianion; OHm2CA, 5-hydroxy-isophthalic acid dianion; Me4bpz, 3,3′,5,5′-tetramethyl-4,4′-bipyrazole], were obtained from acetate hydrates of Ag+, Zn2+, and Cd2+ and mixed ligand systems consisting of Me4bpz and the respective aromatic dicarboxylic acid by means of hydrothermal synthesis. The compounds were characterized by means of X-ray single-crystal structure analysis, elemental analysis, and IR spectroscopy. The topologies realized in these coordination polymers vary from simple one-dimensional polymers to complex three-dimensional frameworks. Hydrogen bonds of different types with influence on the resulting structures are observed in all compounds

Solid-State Ring-Opening Structural Transformation in Triazolyl Ethanesulfonate Based Silver Complexes

Synthesis and crystal structures of distinctive examples of cage-like silver complexes [Ag₆<b>L</b>₆]·9H₂O (<b>1</b>) and [Ag₆<b>L</b>₆(H₂O)₄]·4H₂O (<b>2</b>) (<b>L</b>^<b>–</b> = 2-(4<i>H</i>-1,2,4-triazol-4-yl)­ethanesulfonate) are reported. Both undergo solid-state structural transformation to the one-dimensional polymeric complex [Ag<b>L</b>]_<i>n</i> (<b>3</b>) via a ring-opening process. This transformation is initiated by the release of lattice water molecules and involves opening of nine-membered Ag₃N₆ rings via bond breaking followed by rearrangement of the Ag⁺ coordination sphere by formation of new bonds. These structural transformations were studied by thermogravimetric analysis and single-crystal and powder X-ray diffraction methods. Formation of compounds <b>1</b>, <b>2</b>, and {[Ag<b>L</b>]·1.5 H₂O}_<i>n</i> (<b>4</b>) with the same Ag⁺/<b>L</b>^<b>–</b> ratio but different crystal structures depends on the concentration and acidity of the reaction mixture. Furthermore, ligand conformation and trz-Ag-trz placement (trans, cis, gauche) are important for the connectivity and formation of the coordination polymers