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Here, we present the structural expansion of chalcogenido germanate(IV) or stannate(IV) architectures with Sb<jats:sup>III<\/jats:sup>, which clearly affects the vibrational and optical absorption properties of the solid compounds. For the synthesis of the title compounds, [K<jats:sub>4<\/jats:sub>(H<jats:sub>2<\/jats:sub>O)<jats:sub>4<\/jats:sub>][Ge<jats:sub>4<\/jats:sub>S<jats:sub>10<\/jats:sub>] or [K<jats:sub>4<\/jats:sub>(H<jats:sub>2<\/jats:sub>O)<jats:sub>4<\/jats:sub>][SnS<jats:sub>4<\/jats:sub>] were reacted with SbCl<jats:sub>3<\/jats:sub> under ionothermal conditions in imidazolium\u2010based ionic liquids. Salt metathesis at relatively low temperatures (120\u2009\u00b0C or 150\u2009\u00b0C) enabled the incorporation of (formally) Sb<jats:sup>3+<\/jats:sup> ions into the anionic substructure of the precursors, and their modification to form (Cat)<jats:sub>16<\/jats:sub>[Ge<jats:sub>2<\/jats:sub>Sb<jats:sub>2<\/jats:sub>S<jats:sub>7<\/jats:sub>]<jats:sub>6<\/jats:sub>[GeS<jats:sub>4<\/jats:sub>] (<jats:bold>1<\/jats:bold>) and (Cat)<jats:sub>6<\/jats:sub>[Sn<jats:sub>10<\/jats:sub>O<jats:sub>4<\/jats:sub>S<jats:sub>20<\/jats:sub>][Sb<jats:sub>3<\/jats:sub>S<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub> (<jats:bold>2\u2009a<\/jats:bold> and <jats:bold>2\u2009b<\/jats:bold>), wherein Cat=(C<jats:sub>4<\/jats:sub>C<jats:sub>1<\/jats:sub>C<jats:sub>1<\/jats:sub>Im)<jats:sup>+<\/jats:sup> (<jats:bold>1<\/jats:bold> and <jats:bold>2\u2009a<\/jats:bold>) or (C<jats:sub>4<\/jats:sub>C<jats:sub>1<\/jats:sub>C<jats:sub>2<\/jats:sub>Im)<jats:sup>+<\/jats:sup> (<jats:bold>2\u2009b<\/jats:bold>). In <jats:bold>1<\/jats:bold>, germanium and antimony atoms are combined to form a rare noradamantane\u2010type ternary molecular anion, six of which surround an {GeS<jats:sub>4<\/jats:sub>} unit in a highly symmetric secondary structure, and finally crystallize in a diamond\u2010like superstructure. In <jats:bold>2<\/jats:bold>, supertetrahedral oxo\u2010sulfido stannate clusters are generated, as known from the ionothermal treatment of the stannate precursor alone, yet, linked here into unprecedented one\u2010dimensional strands with {Sb<jats:sub>3<\/jats:sub>S<jats:sub>4<\/jats:sub>} units as linkers. We discuss the single\u2010crystal structures of these uncommon salts of ternary and quaternary chalcogenido (semi)metalate anions, as well as their Raman and UV\u2010visible spectra.<\/jats:p>","DOI":"10.1002\/chem.202003887","type":"journal-article","created":{"date-parts":[[2020,9,2]],"date-time":"2020-09-02T09:37:49Z","timestamp":1599039469000},"page":"16683-16689","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Structural Expansion of Chalcogenido Tetrelates in Ionic Liquids by Incorporation of Sulfido Antimonate Units"],"prefix":"10.1002","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9189-8079","authenticated-orcid":false,"given":"Bertram","family":"Peters","sequence":"first","affiliation":[{"name":"Fachbereich Chemie und Wissenschaftliches Zentrum f\u00fcr, Materialwissenschaften (WZMW) Philipps-Universit\u00e4t Marburg  Hans-Meerwein-Stra\u00dfe 4 35043 Marburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chlo\u00e9","family":"Krampe","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie und Wissenschaftliches Zentrum f\u00fcr, Materialwissenschaften (WZMW) Philipps-Universit\u00e4t Marburg  Hans-Meerwein-Stra\u00dfe 4 35043 Marburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Julian","family":"Kl\u00e4rner","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie und Wissenschaftliches Zentrum f\u00fcr, Materialwissenschaften (WZMW) Philipps-Universit\u00e4t Marburg  Hans-Meerwein-Stra\u00dfe 4 35043 Marburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1325-9228","authenticated-orcid":false,"given":"Stefanie","family":"Dehnen","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie und Wissenschaftliches Zentrum f\u00fcr, Materialwissenschaften (WZMW) Philipps-Universit\u00e4t Marburg  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