Exploratory Synthesis in Molten Salts:  Role of Flux Basicity in the Stabilization of the Complex Thiogermanates Cs4Pb4Ge5S16, K2PbGe2S6, and K4Sn3Ge3S14

Palchik, O.; Marking, G. M.; Kanatzidis, Mercouri G.

doi:10.1021/ic050087v

Cited by 35 publications

(22 citation statements)

References 27 publications

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“…Furthermore, the properties of these fluxes (basicity, viscosity, etc.) can be fine-tuned by adjusting the sulfur content, as shown by Durichen and Bensch 15 as well as by Palchik et al 16 In this paper, we report on the facilitated synthesis of the thiogallates Cs 2 Ga 2 S 5 5 and CsGaS 3 , 3 as well as the reactivity of thiogallates in molten polysulfide fluxes and at elevated temperatures. In order to elucidate the product formation in the polysulfide melts, the reactions were investigated in situ by high-temperature Raman spectroscopy.…”

Section: ■ Introductionmentioning

confidence: 63%

Interconversion of One-Dimensional Thiogallates Cs₂[Ga₂(S₂)_2–xS_2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Friedrich

Schlösser

Pfitzner

2017

Crystal Growth & Design

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The potential of cesium polysulfide-flux reactions for the synthesis of chalcogenogallates was investigated by using X-ray diffraction and Raman spectroscopy. An investigation of possible factors influencing the product formation revealed that only the polysulfide content x in the Cs 2 S x melts has an influence on the crystalline reaction product. From sulfur-rich melts (x > 7), CsGaS 3 is formed, whereas sulfur-poor melts (x < 7) lead to the formation of Cs 2 Ga 2 S 5 . In situ investigations using hightemperature Raman spectroscopy revealed that the crystallization of these solids takes place upon cooling of the melts. Upon heating, CsGaS 3 and Cs 2 Ga 2 S 5 release gaseous sulfur due to the degradation of S 2 2− units. This decomposition of CsGaS 3 to Cs 2 Ga 2 S 5 and finally to CsGaS 2 -mC16 was further studied in situ by using high-temperature X-ray powder diffraction. A combination of the polysulfide reaction route and the high-temperature decomposition leads to the possibility of the directed interconversion of these thiogallates. The presence of disulfide units in the anionic substructures of these thiogallates has a significant influence on the electronic band structures and their optical properties. This influence was studied by using UV/vis-diffuse reflectance spectroscopy and DFT simulations, revealing a trend of smaller band gaps with increasing S 2 2− content. ■ INTRODUCTIONGroup 13 chalcogenometallates containing alkali metal cations M x T y Q z (M = alkali metal, T = triel, Q = chalcogen) are interesting materials due to their semiconducting properties. These materials are used, e.g., in gas sensors or detectors for high-energy radiation. 1 The crystal structures of most compounds in the ternary systems M−T−Q consist of oligomeric or polymeric one-, two-, or three-dimensional (1D, 2D, 3D) anions formed by condensed TQ 4 tetrahedra. 2 Among the large number of chalcogenotrielates, however, only a few compounds featuring polychalcogenide units are known. Incorporation of polychalcogenide units into the anionic structures leads to more exotic structural motives. The crystal structures of mixed-valent chalcogenometallates like CsGaQ 3 , 3,4 Cs 2 Ga 2 Q 5 , 5,6 CsAlTe 3 7 and several chalcogenoborates 8−11 show 1D anionic chains containing Q 2 2− or Q 3 2− units (Q = S, Se). The mixed-valent nature of the chalcogen in these compounds should significantly influence the properties of these semiconductors. Therefore, it is necessary to understand the reactive behavior of these compounds and the conditions necessary for their formation in order to design compounds with desired properties. Molten polysulfide fluxes are an established method for the synthesis of substances featuring polysulfide anions. 12−14 Due to an enhanced diffusion rate at comparably low temperatures in these fluxes, the formation of thermodynamically metastable compounds is favored as compared to high-temperature reactions. Furthermore, the properties of these fluxes (basicity, viscosity, etc.) can be fine-tuned by adjusti...

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Section: ■ Introductionmentioning

confidence: 63%

Interconversion of One-Dimensional Thiogallates Cs₂[Ga₂(S₂)_2–xS_2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Friedrich

Schlösser

Pfitzner

2017

Crystal Growth & Design

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“…4À [17] or [Sn 36 Ge 24 Se 132 ] 24À , [18] indicate the different behavior of the two elements; herein, the germanium atoms are restricted to a coordination number of 4, whereas the tin atoms possess coordination numbers of 5 or 6. As a matter of fact, the condensation of Cl 3 GeR 1 with (Me 3 Si) 2 S does not lead to the formation of complexes with defect heterocubane scaffolds, but rather directly yields the known sesquichalcogenides.…”

Section: Resultsmentioning

confidence: 99%

Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

Eußner

Barth

Leusmann

et al. 2013

Chemistry A European J

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The synthesis of new functionalized organotin-chalcogenide complexes was achieved by systematic optimization of the reaction conditions. The structures of compounds [(R(1, 2) Sn)3 S4 Cl] (1, 2), [((R(2) Sn)2 SnS4 )2 (μ-S)2 ] (3), [(R(1, 2) Sn)3 Se4 ][SnCl3 ] (4, 5), and [Li(thf)n ][(R(3) Sn)(HR(3) Sn)2 Se4 Cl] (6), in which R(1) =CMe2 CH2 C(O)Me, R(2) =CMe2 CH2 C(NNH2 )Me, and R(3) =CH2 CH2 COO, are based on defect heterocubane scaffolds, as shown by X-ray diffraction, (119) Sn NMR spectroscopy, and ESI mass spectrometry analyses. Compounds 4, 5, and 6 constitute the first examples of defect heterocubane-type metal-chalcogenide complexes that are comprised of selenide ligands. Comprehensive DFT calculations prompted us to search for the formal intermediates [(R(1) SnCl2 )2 (μ-S)] (7) and [(R(1) SnCl)2 (μ-S)2 ] (8), which were isolated and helped to understand the stepwise formation of compounds 1-6.

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“…Many of the above building blocks, when stabilized in the presence of lanthanide and alkali cations yield a variety of structures in which the lanthanide-chalcogenide networks can be either two-dimensional or three-dimensional; often the alkali metal cations are found in the inter-layer space of the twodimensional structures [16][17][18][19][20][21][22] or coordinated in the channels of the three dimensional structures [23][24][25][26][27]. Combining these building blocks and lanthanides into a variety of different structure types has yielded a host of compounds displaying interesting materials properties such as semiconductivity, magnetism, and luminescence [18,22,27].…”

Section: Introductionmentioning

confidence: 99%

Structural, optical, and magnetic properties of Na8Eu2(Si2S6)2 and Na8Eu2(Ge2S6)2: Europium(II) quaternary chalcogenides that contain an ethane-like (Si2S6)6− or (Ge2S6)6− moiety

Choudhury

Ghosh

Grandjean

et al. 2015

Journal of Solid State Chemistry

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Exploratory Synthesis in Molten Salts: Role of Flux Basicity in the Stabilization of the Complex Thiogermanates Cs₄Pb₄Ge₅S₁₆, K₂PbGe₂S₆, and K₄Sn₃Ge₃S₁₄

Cited by 35 publications

References 27 publications

Interconversion of One-Dimensional Thiogallates Cs₂[Ga₂(S₂)_2–xS_2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Interconversion of One-Dimensional Thiogallates Cs₂[Ga₂(S₂)_2–xS_2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

Structural, optical, and magnetic properties of Na8Eu2(Si2S6)2 and Na8Eu2(Ge2S6)2: Europium(II) quaternary chalcogenides that contain an ethane-like (Si2S6)6− or (Ge2S6)6− moiety

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Exploratory Synthesis in Molten Salts: Role of Flux Basicity in the Stabilization of the Complex Thiogermanates Cs4Pb4Ge5S16, K2PbGe2S6, and K4Sn3Ge3S14

Cited by 35 publications

References 27 publications

Interconversion of One-Dimensional Thiogallates Cs2[Ga2(S2)2–xS2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Interconversion of One-Dimensional Thiogallates Cs2[Ga2(S2)2–xS2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

Structural, optical, and magnetic properties of Na8Eu2(Si2S6)2 and Na8Eu2(Ge2S6)2: Europium(II) quaternary chalcogenides that contain an ethane-like (Si2S6)6− or (Ge2S6)6− moiety

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Exploratory Synthesis in Molten Salts: Role of Flux Basicity in the Stabilization of the Complex Thiogermanates Cs₄Pb₄Ge₅S₁₆, K₂PbGe₂S₆, and K₄Sn₃Ge₃S₁₄

Interconversion of One-Dimensional Thiogallates Cs₂[Ga₂(S₂)_2–xS_2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions

Interconversion of One-Dimensional Thiogallates Cs₂[Ga₂(S₂)_2–xS_2+x] (x = 0, 1, 2) by Using High-Temperature Decomposition and Polysulfide-Flux Reactions