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Photophysical measurements reveal blue\u2010green emission with a maximum at 520\u2005nm, 32\u2009% quantum yield, and 2430\u2005ns long\u2010lived excited state decay lifetime in deaerated dichloromethane solution. Coordination of lanthanoid ions to the terpyridine units red\u2010shifts the emission to 570\u2005nm and also reveals efficient (90\u2009%) and fast sensitisation of both Eu(III) and Yb(III) at room temperature, with a similar rate constant <jats:italic>k<jats:sub>ET<\/jats:sub><\/jats:italic> on the order of 10<jats:sup>7<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>. Efficient sensitisation of Eu(III) from Re(I) is unprecedented, especially when considering the close proximity in energy between the donor and acceptor excited states. On the other hand, comparative measurements at 77\u2005K reveal that energy transfer to Yb(III) is two orders of magnitude slower than that to Eu(III). A two\u2010step mechanism of sensitisation is therefore proposed, whereby the rate\u2010determining step is a thermally activated energy transfer step between the Re(I) centre and the terpyridine functionality, followed by rapid energy transfer to the respective Ln(III) excited states. At 77\u2005K, the direct Re(I) to Eu(III) energy transfer seems to proceed via a ligand\u2010mediated superexchange Dexter\u2010type mechanism.<\/jats:p>","DOI":"10.1002\/chem.202401233","type":"journal-article","created":{"date-parts":[[2024,6,3]],"date-time":"2024-06-03T00:09:27Z","timestamp":1717373367000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Elucidating the Mechanism of Efficient Eu(III) and Yb(III) Sensitisation from a Re(I) Tetrazolato Triangular Assembly"],"prefix":"10.1002","volume":"30","author":[{"given":"Phillip J.","family":"Wright","sequence":"first","affiliation":[{"name":"School of Molecular and Life Sciences Curtin University  Perth WA 6102 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2270-7141","authenticated-orcid":false,"given":"Michael C.","family":"Pfrunder","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences University of Queensland  Brisbane QLD 4072 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8142-2656","authenticated-orcid":false,"given":"Isaac M.","family":"Etchells","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences University of Queensland  Brisbane QLD 4072 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mohammad A.","family":"Haghighatbin","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Physics La Trobe University  Melbourne VIC 3086 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0692-0505","authenticated-orcid":false,"given":"Paolo","family":"Raiteri","sequence":"additional","affiliation":[{"name":"School of Molecular and Life Sciences Curtin University  Perth WA 6102 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5317-1637","authenticated-orcid":false,"given":"Mark I.","family":"Ogden","sequence":"additional","affiliation":[{"name":"School of Molecular and Life Sciences Curtin University  Perth WA 6102 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7260-4845","authenticated-orcid":false,"given":"Stefano","family":"Stagni","sequence":"additional","affiliation":[{"name":"Department of Industrial Chemistry \u201cToso Montanari\u201d University of Bologna  Bologna 40136 Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8250-3098","authenticated-orcid":false,"given":"Conor F.","family":"Hogan","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Physics La Trobe University  Melbourne VIC 3086 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6710-2322","authenticated-orcid":false,"given":"Lee J.","family":"Cameron","sequence":"additional","affiliation":[{"name":"School of Molecular and Life Sciences Curtin University  Perth WA 6102 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7032-2062","authenticated-orcid":false,"given":"Evan G.","family":"Moore","sequence":"additional","affiliation":[{"name":"School of Chemistry and Molecular Biosciences University of Queensland  Brisbane QLD 4072 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6949-4019","authenticated-orcid":false,"given":"Massimiliano","family":"Massi","sequence":"additional","affiliation":[{"name":"School of Molecular and Life Sciences Curtin University  Perth WA 6102 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,8,12]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/B905604C"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3sc22126a"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00310K"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3RA00991B"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41427-018-0012-y"},{"key":"e_1_2_8_6_1","volume-title":"Basics of Lanthanide Photophysics, Vol. 7","author":"B\u00fcnzli J.-C. 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