{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T13:00:18Z","timestamp":1790600418204,"version":"4.1.0"},"reference-count":80,"publisher":"American Chemical Society (ACS)","issue":"9","license":[{"start":{"date-parts":[[2026,8,19]],"date-time":"2026-08-19T00:00:00Z","timestamp":1787097600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000165","name":"Division of Chemistry","doi-asserted-by":"publisher","award":["CHE-2452948"],"award-info":[{"award-number":["CHE-2452948"]}],"id":[{"id":"10.13039\/100000165","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,28]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Lindqvist-type polyoxovanadate-alkoxides are used as atomically precise, soluble analogs of metal oxides to interrogate site-dependent (e.g., \u03bc2-oxido vs terminal oxido) tunneling in proton-coupled electron transfer (PCET). Variable-temperature kinetic isotope effect (VT-KIE) analysis reveals that H atom uptake at the \u03bc2-oxido site of [TBA]2[V6O8(OCH3)11] proceeds via quantum mechanical tunneling in acetonitrile, evidenced by a temperature-independent KIE, a small isotopic effect on activation energy, and positive Arrhenius prefactor ratio. This behavior is in contrast to PCET at the terminal vanadyl site of [TBA][V6O7(OCH3)12], which follows a semiclassical, concerted proton\u2013electron transfer mechanism. Tunneling effects are solvent dependent; switching to dimethylformamide, a more basic solvent, results in a reduction in H-bonding interactions with the acceptor, lowering the observed rate of H atom uptake at the bridging site. This work highlights the role of site-specific basicity on tunneling in metal oxides, where competitive H-bonding with solvent disrupts tunneling.<\/jats:p>","DOI":"10.1021\/jacsau.6c00947","type":"journal-article","created":{"date-parts":[[2026,8,19]],"date-time":"2026-08-19T20:01:18Z","timestamp":1787169678000},"page":"5287-5294","source":"Crossref","is-referenced-by-count":0,"title":["Evidence for Site-Specific\nTunneling in H Atom Uptake\nat the Surface of Polyoxovanadate-Alkoxides"],"prefix":"10.1021","volume":"6","author":[{"given":"M. Rebecca A.","family":"Walls","sequence":"first","affiliation":[{"name":"University of Rochester , , , ,","place":["Rochester, New York, United States, 14627"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2648-6702","authenticated-orcid":true,"given":"Shannon E.","family":"Cooney","sequence":"additional","affiliation":[{"name":"University of Rochester , , , ,","place":["Rochester, New York, United States, 14627"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3753-8288","authenticated-orcid":true,"given":"Ellen M.","family":"Matson","sequence":"additional","affiliation":[{"name":"University of Rochester , , , ,","place":["Rochester, New York, United States, 14627"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,19]]},"reference":[{"key":"2026092808091976200_cit1","doi-asserted-by":"publisher","first-page":"363","DOI":"10.1146\/annurev.physchem.55.091602.094446","article-title":"PROTON-COUPLED\nELECTRON TRANSFER: A Reaction Chemist\u2019s View","volume":"55","author":"Mayer","year":"2004","journal-title":"Annu. 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