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Here, three phosphomolybdate hybrid compounds have been successfully isolated by the hydrothermal method and been applied as supramolecular catalysts for the reduction of Cr<jats:sup>VI<\/jats:sup>. Single-crystal X-ray diffraction revealed their formulae as (H<jats:sub>2<\/jats:sub>bpp)<jats:sub>2<\/jats:sub>[Fe(H<jats:sub>2<\/jats:sub>O)][Sr(H<jats:sub>2<\/jats:sub>O)<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub>{Fe[Mo<jats:sub>6<\/jats:sub>O<jats:sub>12<\/jats:sub>(OH)<jats:sub>3<\/jats:sub>(H<jats:sub>2<\/jats:sub>PO<jats:sub>4<\/jats:sub>)(HPO<jats:sub>4<\/jats:sub>)(PO<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub>}\u00b75H<jats:sub>2<\/jats:sub>O (<jats:bold>1<\/jats:bold>), (H<jats:sub>2<\/jats:sub>bpp)<jats:sub>2<\/jats:sub>[Na(H<jats:sub>2<\/jats:sub>O)(OC<jats:sub>2<\/jats:sub>H<jats:sub>5<\/jats:sub>)][Fe(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>][Ca(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub>{Fe[Mo<jats:sub>6<\/jats:sub>O<jats:sub>12<\/jats:sub>(OH)<jats:sub>3<\/jats:sub>(H<jats:sub>2<\/jats:sub>PO<jats:sub>4<\/jats:sub>)(HPO<jats:sub>4<\/jats:sub>)(PO<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sub>2<\/jats:sub>}\u00b74H<jats:sub>2<\/jats:sub>O (<jats:bold>2<\/jats:bold>) and (H<jats:sub>2<\/jats:sub>bpe)<jats:sub>3<\/jats:sub>{Fe[Mo<jats:sub>6<\/jats:sub>O<jats:sub>12<\/jats:sub>(OH)<jats:sub>3<\/jats:sub>(HPO<jats:sub>4<\/jats:sub>)<jats:sub>3<\/jats:sub>(H<jats:sub>2<\/jats:sub>PO<jats:sub>4<\/jats:sub>)]<jats:sub>2<\/jats:sub>}\u00b78H<jats:sub>2<\/jats:sub>O (<jats:bold>3<\/jats:bold>) [bpp is 1,3-bis(pyridin-4-yl)propane (C<jats:sub>13<\/jats:sub>H<jats:sub>14<\/jats:sub>N<jats:sub>2<\/jats:sub>) and bpe is <jats:italic>trans<\/jats:italic>-1,2-bis(pyridin-4-yl)ethylene (C<jats:sub>12<\/jats:sub>H<jats:sub>10<\/jats:sub>N<jats:sub>2<\/jats:sub>)]. The three hybrids consist of supramolecular networks built up by noncovalent interactions between {Fe[P<jats:sub>4<\/jats:sub>Mo<jats:sub>6<\/jats:sub>\n                  <jats:sup>V<\/jats:sup>O<jats:sub>31<\/jats:sub>]<jats:sub>2<\/jats:sub>}<jats:sup>22\u2212<\/jats:sup> polyanions and protonated organic cations. This kind of hybrid polyoxometalate could be applied as heterogeneous molecular catalysts for the reduction of Cr<jats:sup>VI<\/jats:sup>. It was found that the organic moiety plays a vital role in influencing the catalytic activity of the polyanions. Organic bpp-containing hybrids <jats:bold>1<\/jats:bold> and <jats:bold>2<\/jats:bold> are highly active in the catalytic reduction of heavy metal Cr<jats:sup>VI<\/jats:sup> ions using HCOOH as reductant, while bpe-containing hybrid <jats:bold>3<\/jats:bold> is inactive to this reaction. This work is significant for the design of new catalysts, as well as the exploration of reaction mechanisms at a molecular level.<\/jats:p>","DOI":"10.1107\/s2053229618013025","type":"journal-article","created":{"date-parts":[[2018,10,18]],"date-time":"2018-10-18T14:21:21Z","timestamp":1539872481000},"page":"1310-1324","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":7,"title":["Crystal structures of hybrid completely reduced phosphomolybdates and catalytic performance applied as molecular catalysts for the reduction of chromium(VI)"],"prefix":"10.1107","volume":"74","author":[{"given":"Xuerui","family":"Tian","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xing","family":"Xin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yuanzhe","family":"Gao","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dandan","family":"Dai","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jinjin","family":"Huang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Zhangang","family":"Han","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2018,10,18]]},"reference":[{"key":"jr3018_bb1","unstructured":"Bruker (2008). 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