A Series of Lanthanide Chalcogenidogermanates Displaying Two Types of 1-D Polymeric Chains

Rational synthesis of inorganic matter remains a great challenge encountered with modern synthetic chemistry. Here we reported the stepwise solvothermal conversion from GeO2 to [MGe4S10] n 3n– (M = Cu, Ag) polymer via isolatable [Ge2S6]4– and [Ge4S10]4– anions by virtue of templating technique. The facile sulfuration of GeO2 resulted in the methylammonium-templated dimeric thiogermanate [CH3NH3]4Ge2S6 (1). This was used subsequently as a precursor for the formation of adamantane-like [Ge4S10]4– cluster, which was isolated as a mixed methylammonium/ethylammonium salt [CH3CH2NH3]3[CH3NH3]Ge4S10 (2). Compound 2 was then successfully used as a precursor to react with Cu+ and Ag+ cations in the presence of tetraethylammonium, resulting in alternating copolymeric products [(CH3CH2)4N]3MGe4S10 (M = Cu (3), Ag (4)), whose anionic moieties feature a novel zigzag chainlike structure constructed by [Ge4S10]4– clusters via two-coordinate Cu+/Ag+ linkers. Mixed amine/ethanol or deep eutectic solvents were applied as media for the syntheses of 1–4, and all the products were characterized in the solid state and solution. Crystal structural analysis of the title compounds revealed significant templating roles of the alkylammonium cations as both space-filling agents and hydrogen-bonding donors, suggesting the structure-directing mechanism for the species formation and crystal growth. The design and optimization of multistep structural conversion upon templating effects would be beneficial for drawing rational, predictable pathways for inorganic synthesis.

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“…These bond distances and angles match well with those of other reported analogues containing [Ge 2 S 6 ] 4– anions (as listed in Table S1). ,− …”

Section: Results and Discussionmentioning

confidence: 99%

Stepwise Conversion from GeO₂ to [MGe₄S₁₀]_n^3n– (M = Cu, Ag) Polymer via Isolatable [Ge₂S₆]^4– and [Ge₄S₁₀]^4– Anions by Virtue of Templating Technique

et al. 2019

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Tris(ethylenediamine)nickel(II) thio-hydroxogermanate monohydrate: Synthesis, crystal structure, 1H NMR, EPR, optical and magnetic properties

Alahmari

Davaasuren

Emwas

et al. 2019

Inorganica Chimica Acta

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An Organic Hybrid Indium–Telluride Incorporating Binuclear Complexes [In₂(ea)₄]²⁺ with a Bridging Oxygen Donor

Liu

Shan

et al. 2021

Inorg. Chem.

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The new organic hybrid indium−telluride [In 2 (ea) 2 Te 2 ] n (1; Hea = ethanolamine) exhibits a new type of onedimensional polymeric chain based on the linkages of dinuclear [In 2 (ea) 4 ] 2+ and [In 2 Te 4 ] 2− units, which offers the first example of an indium−telluride framework incorporating binuclear complexes [In 2 (ea) 4 ] 2+ with a bridging O donor. 1 shows a distinctive photocurrent response and photocatalytic properties under visible-light illumination.

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A Series of Lanthanide Chalcogenidogermanates Displaying Two Types of 1-D Polymeric Chains

Cited by 3 publications

References 45 publications

Stepwise Conversion from GeO₂ to [MGe₄S₁₀]_n^3n– (M = Cu, Ag) Polymer via Isolatable [Ge₂S₆]^4– and [Ge₄S₁₀]^4– Anions by Virtue of Templating Technique

Stepwise Conversion from GeO₂ to [MGe₄S₁₀]_n^3n– (M = Cu, Ag) Polymer via Isolatable [Ge₂S₆]^4– and [Ge₄S₁₀]^4– Anions by Virtue of Templating Technique

Tris(ethylenediamine)nickel(II) thio-hydroxogermanate monohydrate: Synthesis, crystal structure, 1H NMR, EPR, optical and magnetic properties

An Organic Hybrid Indium–Telluride Incorporating Binuclear Complexes [In₂(ea)₄]²⁺ with a Bridging Oxygen Donor

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A Series of Lanthanide Chalcogenidogermanates Displaying Two Types of 1-D Polymeric Chains

Cited by 3 publications

References 45 publications

Stepwise Conversion from GeO2 to [MGe4S10]n3n– (M = Cu, Ag) Polymer via Isolatable [Ge2S6]4– and [Ge4S10]4– Anions by Virtue of Templating Technique

Stepwise Conversion from GeO2 to [MGe4S10]n3n– (M = Cu, Ag) Polymer via Isolatable [Ge2S6]4– and [Ge4S10]4– Anions by Virtue of Templating Technique

Tris(ethylenediamine)nickel(II) thio-hydroxogermanate monohydrate: Synthesis, crystal structure, 1H NMR, EPR, optical and magnetic properties

An Organic Hybrid Indium–Telluride Incorporating Binuclear Complexes [In2(ea)4]2+ with a Bridging Oxygen Donor

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Stepwise Conversion from GeO₂ to [MGe₄S₁₀]_n^3n– (M = Cu, Ag) Polymer via Isolatable [Ge₂S₆]^4– and [Ge₄S₁₀]^4– Anions by Virtue of Templating Technique

Stepwise Conversion from GeO₂ to [MGe₄S₁₀]_n^3n– (M = Cu, Ag) Polymer via Isolatable [Ge₂S₆]^4– and [Ge₄S₁₀]^4– Anions by Virtue of Templating Technique

An Organic Hybrid Indium–Telluride Incorporating Binuclear Complexes [In₂(ea)₄]²⁺ with a Bridging Oxygen Donor