{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,18]],"date-time":"2026-06-18T23:26:10Z","timestamp":1781825170599,"version":"3.54.5"},"reference-count":15,"publisher":"Wiley","issue":"6","license":[{"start":{"date-parts":[[2025,1,20]],"date-time":"2025-01-20T00:00:00Z","timestamp":1737331200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["17\u201073\u201010413"],"award-info":[{"award-number":["17\u201073\u201010413"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Photochem &amp;amp; Photobiology"],"published-print":{"date-parts":[[2025,11]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Recently (\n                    <jats:italic>Photochem Photobiol<\/jats:italic>\n                    . 2023;100:1277\u20131289. doi:\n                    <jats:ext-link xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"https:\/\/doi.org\/10.1111\/php.13898\">10.1111\/php.13898<\/jats:ext-link>\n                    ), we described the anti\u2010Kasha effect in tribenzo\u20106\n                    <jats:italic>H<\/jats:italic>\n                    \u20101,4\u2010diazepinoporphyrazins with\n                    <jats:italic>C<\/jats:italic>\n                    <jats:sub>\n                      <jats:italic>2v<\/jats:italic>\n                    <\/jats:sub>\n                    symmetry, where the ultrafast spin changes successfully compete with the internal conversion. In this study, we show the presence of this effect in 2 (3),9 (10),16(17),23(24)\u2010tetra\u2010\n                    <jats:italic>tert<\/jats:italic>\n                    \u2010butyl\u201029\n                    <jats:italic>H<\/jats:italic>\n                    ,31\n                    <jats:italic>H<\/jats:italic>\n                    \u2010phthalocyanine (\n                    <jats:bold>1<\/jats:bold>\n                    ) and 1,4\u2010di\u2010[2\u2010(2\u2010methoxyethoxy)ethoxy]\u201029\n                    <jats:italic>H<\/jats:italic>\n                    ,31\n                    <jats:italic>H<\/jats:italic>\n                    \u2010phthalocyanine (\n                    <jats:bold>2<\/jats:bold>\n                    ), which also possess reduced molecular symmetry and do not bear 6\n                    <jats:italic>H<\/jats:italic>\n                    \u20101,4\u2010diazepine fragments. The anti\u2010Kasha effect in\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    supplemented by Mg(II) tribenzo\u20106\n                    <jats:italic>H<\/jats:italic>\n                    \u20101,4\u2010diazepinoporphyrazinates\n                    <jats:bold>3<\/jats:bold>\n                    and\n                    <jats:bold>4<\/jats:bold>\n                    exhibits a close\u2010to\u2010linear dependence on energy gap value between the zero vibrational levels of two lowest singlet excited states S\n                    <jats:sub>1<\/jats:sub>\n                    <jats:sup>0<\/jats:sup>\n                    and S\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>0<\/jats:sup>\n                    (these states are degenerate in\n                    <jats:italic>D<\/jats:italic>\n                    <jats:sub>\n                      <jats:italic>4h<\/jats:italic>\n                    <\/jats:sub>\n                    symmetry) and enhances with increase. The theoretical kinetic model of excited state dynamics, which takes into account the observed effects and follows Fermi's golden rule, predicts the presence of an additional excited state with enhanced spin\u2010orbit coupling compared to S\n                    <jats:sub>1<\/jats:sub>\n                    <jats:sup>0<\/jats:sup>\n                    , S\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>0<\/jats:sup>\n                    and the corresponding triplet states, which is not predicted by TDDFT calculations in the Born\u2013Oppenheimer approximation. The combination of the above indicates that the key role in the observed anti\u2010Kasha effect and the mechanism of dissipation of the excited state in porphyrazines and their analogs is played by vibronic excited states, which requires theoretical research methods beyond the Born\u2013Oppenheimer approximation.\n                  <\/jats:p>","DOI":"10.1111\/php.14064","type":"journal-article","created":{"date-parts":[[2025,1,20]],"date-time":"2025-01-20T05:44:56Z","timestamp":1737351896000},"page":"1402-1406","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Breakdown of the Kasha\u2013Vavilov's rule in low\u2010symmetry porphyrazines: Ultrafast intersystem crossing via high vibronic state"],"prefix":"10.1111","volume":"101","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4718-2775","authenticated-orcid":false,"given":"Pavel A.","family":"Tarakanov","sequence":"first","affiliation":[{"name":"Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry Russian Academy of Sciences (IPAC RAS)  Chernogolovka Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0133-0776","authenticated-orcid":false,"given":"Alexei V.","family":"Kozlov","sequence":"additional","affiliation":[{"name":"Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry Russian Academy of Sciences (FRC PCPMC RAS)  Chernogolovka Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6709-8562","authenticated-orcid":false,"given":"Anton O.","family":"Simakov","sequence":"additional","affiliation":[{"name":"Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry Russian Academy of Sciences (IPAC RAS)  Chernogolovka Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7411-9034","authenticated-orcid":false,"given":"Nikolay S.","family":"Goryachev","sequence":"additional","affiliation":[{"name":"Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry Russian Academy of Sciences (FRC PCPMC RAS)  Chernogolovka Russia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3984-1061","authenticated-orcid":false,"given":"Victor E.","family":"Pushkarev","sequence":"additional","affiliation":[{"name":"Institute of Physiologically Active Compounds at Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry Russian Academy of Sciences (IPAC RAS)  Chernogolovka 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