Different Chemical Environments of [Ge4Se10]4– in the Li+ Compounds [Li4(H2O)16][Ge4Se10]·4.33H2O, [{Li4(thf)12}Ge4Se10], and [Li2(H2O)8][MnGe4Se10], and Ionic Conductivity of Underlying “Li4Ge4Se10”

Duchardt, Marc; Haddadpour, Sima; Kaib, Thomas; Bron, Philipp; Roling, Bernhard; Dehnen, Stefanie

doi:10.1021/acs.inorgchem.1c00225

Cited by 4 publications

(2 citation statements)

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“…They are mostly formed from the elements and/or simple binary precursors by the Methods A–C and E, resulting in regular adamantane-type anions with mostly (alkaline) metal or ammonium counterions. 253–282 In a unique synthetic approach, it was also shown that those clusters can be made electrochemically using a Sn 2 Se 3 cathode in a [Et 4 N]Br electrolyte solution in ethane-1,2-diamine to form [Et 4 N] 4 [Sn 4 Se 10 ] ( 517 ). 283…”

Section: Variety Of Compositions and Synthesesmentioning

confidence: 99%

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Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Rinn,

Rojas-León,

Peerless

et al. 2024

Chem. Sci.

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Section: Variety Of Compositions and Synthesesmentioning

confidence: 99%

“…Two examples also showcase the possibility of creating manganese linked adamantane-type structures by Method E, the extraction of a solid created from a melt of simple precursors ( 1007–1008 ). 275,282 This led to the only example of a tellurium adamantane in network structures ( 1007 ).…”

Section: Variety Of Compositions and Synthesesmentioning

confidence: 99%

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Rinn,

Rojas-León,

Peerless

et al. 2024

Chem. Sci.

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Conductivity in Open-Framework Chalcogenides Tuned via Band Engineering and Redox Chemistry

et al. 2022

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Metrics & MoreArticle Recommendations * sı Supporting Information ABSTRACT: "Open-framework chalcogenides" are an important class of materials that combine porosity with semiconductor behavior, and yet fundamental aspects of their conductivity remain unexplored. Here, we report a combined experimental−computational approach to the iconic subclass of materials TMA 2 MGe 4 Q 10 (TMA = tetramethyl ammonium; M = Mn, Fe, Co, Ni, Zn; Q = S, Se). Direct current (DC) conductivity measurements and density functional theory (DFT) modeling reveal that metal ion and chalcogenide identities dominate key properties of the band structures, while impedance spectroscopy reveals purely electronic band-type transport in the Fe frameworks and redox-type mixed ion−electron conductivity in the others. Redox chemistry and computation suggest that the unique conductivity of Fe arises from its propensity toward Fe 2+ /Fe 3+ mixed valency as a source of ptype doping and from its highly covalent bonds that ensure high carrier mobilities. Taken together, these results demonstrate openframework chalcogenides as a well-defined platform for understanding porous semiconductors and for achieving highly tunable electronic performance.

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Ion-Selective Assembly of Supertetrahedral Selenido Germanate Clusters for Alkali Metal Ion Capture and Separation

Weigend

Fenske

et al. 2023

J. Am. Chem. Soc.

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Supertetrahedral chalcogenido (semi)metalate cluster-based frameworks possess high selectivity for alkali metal cations, matching the specific charge density of their inner surfaces, which enables their use as ion-exchange materials. Aggregates of the supertetrahedral chalcogenido metalate cluster offer even new perspectives for metal ion capture and separation. Herein, we report on ionothermal preparation of two corresponding model compounds, (C 2 C 1 Im) 7 [Cs@Ge II 4 (Ge IV 4 Se 10 ) 4 ] ( 1) and (C 2 C 1 Im) 10 [Na 5 (CN) 6 @Cu 6 (Ge 4 Se 10 ) 4 (Cu)] (2). Their formation is reliant on one specific cation type each, Cs + for 1 and Na + for 2, thus providing promising separation potential during crystallization. Compound 1 is based on the largest discrete binary selenido germanate cluster reported to date and the first mixedvalent chalcogenido germanate(II/IV) supertetrahedron. Moreover, it adds to the few examples of chalcogenides capable of capturing Cs + ions. Its high selectivity for Cs + compared to that of Li + , Na + , K + , and Rb + was confirmed by single-crystal X-ray diffraction, energy-dispersive X-ray spectroscopy, and electrospray ionization mass spectrometry. Quantum chemical studies indicate that smaller ions, K + and Rb + , could also be embedded in an isolated cluster assembly, but as the cluster aggregate slightly distorts for crystallization, the selectivity for Cs + becomes exclusive in the salt. The anionic substructure of compound 2 is based on a twodimensional network of supramolecular assemblies and exhibits an exclusive preference for Na + . This work thus provides the first comprehensive insight into the selective incorporation of specific alkali metal ions into supramolecular aggregates of supertetrahedral chalcogenide clusters, as a promising basis for new ion trapping techniques�especially for heavy alkali metal ions that pose environmental challenges.

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Different Chemical Environments of [Ge₄Se₁₀]^4– in the Li⁺ Compounds [Li₄(H₂O)₁₆][Ge₄Se₁₀]·4.33H₂O, [{Li₄(thf)₁₂}Ge₄Se₁₀], and [Li₂(H₂O)₈][MnGe₄Se₁₀], and Ionic Conductivity of Underlying “Li₄Ge₄Se₁₀”

Cited by 4 publications

References 69 publications

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

Conductivity in Open-Framework Chalcogenides Tuned via Band Engineering and Redox Chemistry

Ion-Selective Assembly of Supertetrahedral Selenido Germanate Clusters for Alkali Metal Ion Capture and Separation

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