{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T02:00:36Z","timestamp":1791252036835,"version":"4.1.0"},"reference-count":69,"publisher":"Wiley","issue":"37","license":[{"start":{"date-parts":[[2020,6,18]],"date-time":"2020-06-18T00:00:00Z","timestamp":1592438400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100002428","name":"Austrian Science Fund","doi-asserted-by":"publisher","award":["P28896"],"award-info":[{"award-number":["P28896"]}],"id":[{"id":"10.13039\/501100002428","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2020,7,2]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The electronic structure and photochemistry of copper formate clusters, Cu<jats:sup>I<\/jats:sup><jats:sub>2<\/jats:sub>(HCO<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub><jats:sup>\u2212<\/jats:sup> and Cu<jats:sup>II<\/jats:sup><jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>(HCO<jats:sub>2<\/jats:sub>)<jats:sub>2<jats:italic>n<\/jats:italic>+1<\/jats:sub><jats:sup>\u2212<\/jats:sup>, <jats:italic>n<\/jats:italic>\u22648, are investigated in the gas phase by using UV\/Vis spectroscopy in combination with quantum chemical calculations. A clear difference in the spectra of clusters with Cu<jats:sup>I<\/jats:sup> and Cu<jats:sup>II<\/jats:sup> copper ions is observed. For the Cu<jats:sup>I<\/jats:sup> species, transitions between copper d and s\/p orbitals are recorded. For stoichiometric Cu<jats:sup>II<\/jats:sup> formate clusters, the spectra are dominated by copper d\u2013d transitions and charge\u2010transfer excitations from formate to the vacant copper d orbital. Calculations reveal the existence of several energetically low\u2010lying isomers, and the energetic position of the electronic transitions depends strongly on the specific isomer. The oxidation state of the copper centers governs the photochemistry. In Cu<jats:sup>II<\/jats:sup>(HCO<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub><jats:sup>\u2212<\/jats:sup>, fast internal conversion into the electronic ground state is observed, leading to statistical dissociation; for charge\u2010transfer excitations, specific excited\u2010state reaction channels are observed in addition, such as formyloxyl radical loss. In Cu<jats:sup>I<\/jats:sup><jats:sub>2<\/jats:sub>(HCO<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub><jats:sup>\u2212<\/jats:sup>, the system relaxes to a local minimum on an excited\u2010state potential\u2010energy surface and might undergo fluorescence or reach a conical intersection to the ground state; in both cases, this provides substantial energy for statistical decomposition. Alternatively, a Cu<jats:sup>II<\/jats:sup>(HCO<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>Cu<jats:sup>0\u2212<\/jats:sup> biradical structure is formed in the excited state, which gives rise to the photochemical loss of a neutral copper atom.<\/jats:p>","DOI":"10.1002\/chem.202000280","type":"journal-article","created":{"date-parts":[[2020,3,10]],"date-time":"2020-03-10T12:48:11Z","timestamp":1583844491000},"page":"8286-8295","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["UV\/Vis Spectroscopy of Copper Formate Clusters: Insight into Metal\u2010Ligand Photochemistry"],"prefix":"10.1002","volume":"26","author":[{"given":"Tobias F.","family":"Pascher","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Ionenphysik und Angewandte Physik Universit\u00e4t Innsbruck  Technikerstra\u00dfe 25 6020 Innsbruck Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4801-3068","authenticated-orcid":false,"given":"Milan","family":"On\u010d\u00e1k","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Ionenphysik und Angewandte Physik Universit\u00e4t Innsbruck  Technikerstra\u00dfe 25 6020 Innsbruck Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0493-820X","authenticated-orcid":false,"given":"Christian","family":"van der Linde","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Ionenphysik und Angewandte Physik Universit\u00e4t Innsbruck  Technikerstra\u00dfe 25 6020 Innsbruck Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9373-9266","authenticated-orcid":false,"given":"Martin K.","family":"Beyer","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Ionenphysik und Angewandte Physik Universit\u00e4t Innsbruck  Technikerstra\u00dfe 25 6020 Innsbruck Austria"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,6,18]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00197"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00816"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201204995"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201204995"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201707098"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201707098"},{"key":"e_1_2_7_5_1","first-page":"731","volume":"70","author":"Royer M. 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