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Herein, five BisTris\u2010modified decavanadate\u2010based coordination polymers were prepared under mild acidic conditions. Compound\n                    <jats:bold>1<\/jats:bold>\n                    is assembled from [V\n                    <jats:sub>10<\/jats:sub>\n                    O\n                    <jats:sub>28<\/jats:sub>\n                    ]\n                    <jats:sup>6\u2212<\/jats:sup>\n                    anions, Na\n                    <jats:sup>+<\/jats:sup>\n                    cations, and BisTris ligands, whereas isostructural compounds\n                    <jats:bold>2<\/jats:bold>\n                    \u2013\n                    <jats:bold>5<\/jats:bold>\n                    incorporate Co\n                    <jats:sup>2+<\/jats:sup>\n                    , Ni\n                    <jats:sup>2+<\/jats:sup>\n                    , Cu\n                    <jats:sup>2+<\/jats:sup>\n                    , or Zn\n                    <jats:sup>2+<\/jats:sup>\n                    centers as BisTris\u2010chelated complex cations. Single\u2010crystal analyses reveal that these transition\u2010metal\u2013BisTris units are integrated with decavanadate\u2013sodium chains through hydrogen\u2010bonding, electrostatic, and, in minor disordered components, Na\u2013O coordination interactions, creating multiple accessible activation sites. In the cycloaddition of CO\n                    <jats:sub>2<\/jats:sub>\n                    with epichlorohydrin, all catalysts afford &gt;99% selectivity under 1 atm CO\n                    <jats:sub>2<\/jats:sub>\n                    at 60\u00b0C, with the Zn\u2010containing compound\n                    <jats:bold>5<\/jats:bold>\n                    giving the highest yield of 98.2%. Compounds\n                    <jats:bold>2<\/jats:bold>\n                    \u2013\n                    <jats:bold>5<\/jats:bold>\n                    outperform the metal\u2010free analogue\n                    <jats:bold>1<\/jats:bold>\n                    , and control experiments with isolated BisTris\u2013Co and decavanadate components confirm a cooperative contribution from vanadium Lewis acid sites, transition\u2010metal centers, and BisTris hydroxyl groups. The best catalyst retains high activity over five cycles and shows broad epoxide tolerance, highlighting a modular strategy for constructing POM\u2010based catalysts for mild CO\n                    <jats:sub>2<\/jats:sub>\n                    fixation.\n                  <\/jats:p>","DOI":"10.1002\/chem.71552","type":"journal-article","created":{"date-parts":[[2026,8,8]],"date-time":"2026-08-08T06:13:43Z","timestamp":1786169623000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Decavanadate Coordination Polymers With Transition\u2010Metal\u2010BisTris Cations for Synergistic Atmospheric CO\n                    <sub>2<\/sub>\n                    Cycloaddition"],"prefix":"10.1002","author":[{"given":"Yin","family":"Zhang","sequence":"first","affiliation":[{"name":"Junior Education Department Changsha Normal University  Changsha Hunan P. R. 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