{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T18:43:26Z","timestamp":1790189006057,"version":"4.1.0"},"reference-count":37,"publisher":"AIP Publishing","issue":"16","funder":[{"DOI":"10.13039\/100006151","name":"Basic Energy Sciences","doi-asserted-by":"publisher","award":["DE-SC0024280"],"award-info":[{"award-number":["DE-SC0024280"]}],"id":[{"id":"10.13039\/100006151","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2025,4,28]]},"abstract":"<jats:p>Solid-state variable-temperature, variable-field magneto-photoluminescence experiments have been performed on the emissive excited triplet state (T1) of the ligand-to-ligand charge transfer (LL\u2032CT) complex (qdt)Pt(dbbpy) (qdt = quinoxaline-2,3-dithiolate; dbbpy = 4,4\u2032-di-tert-butyl-2-2\u2032-bipyridine). We observe a strong temperature and magnetic field dependence of the PL spectra, and the spin\u2013lattice relaxation (T1) among ms levels within the T1 state appears to be accelerated due to both ZFS in the T1 state and the presence of the applied magnetic field, allowing for an assessment of the axial ZFS parameter (D) for the chromophoric T1 state, which is EPR silent at X-band (\u223c9\u00a0GHz). Analysis of the data indicates a zero-field splitting (ZFS) of the T1 state (\u22122.9 \u00b1 0.7\u00a0cm\u22121) that derives from the presence of spin\u2013orbit coupling related to the heavy Pt(II) ion. The results have been used to provide an estimate of the ZFS in the quartet excited state of related radical-elaborated (radical-dichalcogenolene)Pt(dbbpy) complexes. This information is necessary to understand how transitions between the 2T1 and 4T1 excited states in these radical-elaborated complexes lead to electron spin polarization within their 2T1 state and how this is transferred to the 2S0 electronic ground state.<\/jats:p>","DOI":"10.1063\/5.0270046","type":"journal-article","created":{"date-parts":[[2025,4,30]],"date-time":"2025-04-30T09:59:33Z","timestamp":1746007173000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":5,"title":["Excited triplet state zero-field splitting in a ligand-to-ligand charge transfer complex"],"prefix":"10.1063","volume":"162","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0727-2925","authenticated-orcid":false,"given":"Joshua","family":"Mengell","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-2527-0058","authenticated-orcid":false,"given":"Shiyue","family":"Gao","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Caroline","family":"Mangione","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mundendra","family":"Yadav","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dominic","family":"Kersi","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8241-9160","authenticated-orcid":false,"given":"Jing","family":"Yang","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6365-7155","authenticated-orcid":false,"given":"Stephen","family":"McGill","sequence":"additional","affiliation":[{"name":"National High Magnetic Field Laboratory 2 , 1800 E. Paul Dirac Dr., Tallahassee, Florida 32310-3706,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8121-6812","authenticated-orcid":false,"given":"David A.","family":"Shultz","sequence":"additional","affiliation":[{"name":"Department of Chemistry, North Carolina State University 3 , Raleigh, North Carolina 27695-8204,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1479-3318","authenticated-orcid":false,"given":"Martin L.","family":"Kirk","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology, The University of New Mexico 1 , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001,","place":["USA"]},{"name":"Center for Quantum Information and Control (CQuIC), The University of New Mexico 4 , Albuquerque, New Mexico 87131-0001,","place":["USA"]},{"name":"The Center for High Technology Materials, The University of New Mexico 5 , Albuquerque, New Mexico 87106,","place":["USA"]},{"name":"Center for Computational Chemistry, The University of New Mexico 6 , Albuquerque, New Mexico 87131-0001,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,4,30]]},"reference":[{"issue":"13","key":"2025043005592603000_c1","doi-asserted-by":"publisher","first-page":"9285","DOI":"10.1021\/jacs.4c00930","article-title":"Photoinduced magnetic exchange-jump promotes ground state biradical electron spin polarization","volume":"146","year":"2024","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"36","key":"2025043005592603000_c2","doi-asserted-by":"publisher","first-page":"9689","DOI":"10.1039\/d3sc03049k","article-title":"Competitive reversed quartet mechanisms for photogenerated ground state electron spin polarization","volume":"14","year":"2023","journal-title":"Chem. Sci."},{"issue":"46","key":"2025043005592603000_c3","doi-asserted-by":"publisher","first-page":"21005","DOI":"10.1021\/jacs.2c09680","article-title":"Single-photon-induced electron spin polarization of two exchange-coupled stable radicals","volume":"144","year":"2022","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"3","key":"2025043005592603000_c4","doi-asserted-by":"publisher","first-page":"872","DOI":"10.1021\/acs.jpclett.1c03491","article-title":"Excited state exchange control of photoinduced electron spin polarization in electronic ground states","volume":"13","year":"2022","journal-title":"J.\u00a0Phys. Chem. Lett."},{"issue":"41","key":"2025043005592603000_c5","doi-asserted-by":"publisher","first-page":"13704","DOI":"10.1039\/d1sc02965g","article-title":"Chromophore-radical excited state antiferromagnetic exchange controls the sign\u00a0of photoinduced ground state spin polarization","volume":"12","year":"2021","journal-title":"Chem. Sci."},{"issue":"28","key":"2025043005592603000_c6","doi-asserted-by":"publisher","first-page":"10519","DOI":"10.1021\/jacs.1c04149","article-title":"Metal ion control of photoinduced electron spin polarization in electronic ground states","volume":"143","year":"2021","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"6","key":"2025043005592603000_c7","doi-asserted-by":"publisher","first-page":"2221","DOI":"10.1021\/jacs.7b11397","article-title":"Excited state magnetic exchange interactions enable large spin polarization effects","volume":"140","year":"2018","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"9","key":"2025043005592603000_c8","doi-asserted-by":"publisher","first-page":"490","DOI":"10.1038\/s41570-020-0200-5","article-title":"Exploiting chemistry and molecular systems for quantum information science","volume":"4","year":"2020","journal-title":"Nat. Rev. Chem."},{"issue":"5","key":"2025043005592603000_c9","doi-asserted-by":"publisher","first-page":"712","DOI":"10.1021\/acscentsci.0c00737","article-title":"A molecular approach to quantum sensing","volume":"7","year":"2021","journal-title":"ACS Cent. Sci."},{"key":"2025043005592603000_c10","doi-asserted-by":"publisher","first-page":"165534","DOI":"10.1016\/j.jmmm.2019.165534","article-title":"Towards quantum sensing with molecular spins","volume":"491","year":"2019","journal-title":"J.\u00a0Magn. Magn. Mater."},{"issue":"21","key":"2025043005592603000_c11","doi-asserted-by":"publisher","first-page":"13470","DOI":"10.1021\/acs.inorgchem.8b02087","article-title":"Ground state nuclear magnetic resonance chemical shifts predict charge-separated excited state lifetimes","volume":"57","year":"2018","journal-title":"Inorg. Chem."},{"issue":"10","key":"2025043005592603000_c12","doi-asserted-by":"publisher","first-page":"4791","DOI":"10.1021\/ic500217y","article-title":"Ligand control of donor\u2013acceptor excited-state lifetimes","volume":"53","year":"2014","journal-title":"Inorg. Chem."},{"key":"2025043005592603000_c13","first-page":"315","article-title":"Luminescence and photochemistry of metal dithiolene complexes","volume-title":"Progress in Inorganic Chemistry: Synthesis, Properties, and Applications","author":"Stiefel","year":"2004"},{"key":"2025043005592603000_c14","doi-asserted-by":"publisher","first-page":"125","DOI":"10.1016\/S0010-8545(98)90023-6","article-title":"Luminescent platinum complexes: Tuning and using the excited state","volume":"171","year":"1998","journal-title":"Coord. Chem. Rev."},{"key":"2025043005592603000_c15","doi-asserted-by":"publisher","first-page":"1949","DOI":"10.1021\/ja951345y","article-title":"Tuning the excited-state properties of platinum(II) diimine dithiolate complexes","volume":"118","year":"1996","journal-title":"J.\u00a0Am. Chem. Soc."},{"key":"2025043005592603000_c16","doi-asserted-by":"publisher","first-page":"2007","DOI":"10.1021\/ic00112a010","article-title":"Luminescent platinum(II) complexes of quinoxaline-2,3-dithiolate","volume":"34","year":"1995","journal-title":"Inorg. Chem."},{"key":"2025043005592603000_c17","doi-asserted-by":"publisher","first-page":"2913","DOI":"10.1021\/ic00091a034","article-title":"Synthesis and characterization of luminescent square-planar platinum(II) complexes containing dithiolate or dithiocarbamate ligands","volume":"33","year":"1994","journal-title":"Inorg. Chem."},{"key":"2025043005592603000_c18","doi-asserted-by":"publisher","first-page":"237","DOI":"10.1016\/0010-8545(91)84029-5","article-title":"Solvatochromic and emissive properties of Pt(II) complexes with 1,1- and 1,2-ditholates","volume":"111","year":"1991","journal-title":"Coord. Chem. Rev."},{"key":"2025043005592603000_c19","doi-asserted-by":"publisher","first-page":"47","DOI":"10.1016\/0010-8545(90)80079-9","article-title":"Platinum(II) diimine dithiolates. New solution luminescent complexes","volume":"97","year":"1990","journal-title":"Coord. Chem. Rev."},{"issue":"24","key":"2025043005592603000_c20","doi-asserted-by":"publisher","first-page":"8916","DOI":"10.1021\/ja00206a023","article-title":"Square-planar complexes of platinum(II) that luminesce in fluid solution","volume":"111","year":"1989","journal-title":"J.\u00a0Am. Chem. Soc."},{"key":"2025043005592603000_c21","doi-asserted-by":"publisher","first-page":"295","DOI":"10.1002\/9780470166130.ch4","volume":"12","year":"1970","journal-title":"Prog. Inorg. Chem."},{"issue":"9","key":"2025043005592603000_c22","doi-asserted-by":"publisher","first-page":"3986","DOI":"10.1021\/jacs.8b13011","article-title":"Wave function control of charge-separated excited-state lifetimes","volume":"141","year":"2019","journal-title":"J.\u00a0Am. Chem. Soc."},{"key":"2025043005592603000_c23","doi-asserted-by":"publisher","first-page":"107410","DOI":"10.1016\/j.jmr.2023.107410","article-title":"Computational tools for the simulation and analysis of spin-polarized EPR spectra","volume":"349","year":"2023","journal-title":"J.\u00a0Magn. Reson."},{"issue":"3","key":"2025043005592603000_c24","doi-asserted-by":"publisher","first-page":"28","DOI":"10.1063\/PT.3.5196","article-title":"Light-driven spin chemistry for quantum information science","volume":"76","year":"2023","journal-title":"Phys. Today"},{"issue":"98","key":"2025043005592603000_c25","doi-asserted-by":"publisher","first-page":"13773","DOI":"10.1039\/c8cc07939k","article-title":"Progress towards creating optically addressable molecular qubits","volume":"54","year":"2018","journal-title":"Chem. Commun."},{"issue":"15","key":"2025043005592603000_c26","doi-asserted-by":"publisher","first-page":"154305","DOI":"10.1063\/1.5124731","article-title":"A phenomenological scheme for reversed quartet mechanism of electron spin polarization in covalently linked systems of chromophore and free radical: Determination of magnitude of polarization and application to pyrene\u2013TEMPO linked molecules","volume":"151","year":"2019","journal-title":"J.\u00a0Chem. Phys."},{"issue":"49","key":"2025043005592603000_c27","doi-asserted-by":"publisher","first-page":"11144","DOI":"10.1021\/jp0540104","article-title":"Electron spin polarization of functionalized fullerenes. Reversed quartet mechanism","volume":"109","year":"2005","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"2","key":"2025043005592603000_c28","doi-asserted-by":"publisher","first-page":"350","DOI":"10.1021\/ja1070366","article-title":"Sensitizing the sensitizer: The synthesis and photophysical study of bodipy\u2212Pt(II)(diimine)(dithiolate) conjugates","volume":"133","year":"2011","journal-title":"J.\u00a0Am. Chem. Soc."},{"issue":"3","key":"2025043005592603000_c29","doi-asserted-by":"publisher","first-page":"179","DOI":"10.1002\/bio.2342","article-title":"High-field magneto-photoluminescence of semiconductor nanostructures","volume":"27","year":"2012","journal-title":"Luminescence"},{"issue":"8","key":"2025043005592603000_c30","doi-asserted-by":"publisher","first-page":"875","DOI":"10.1016\/j.crci.2008.04.001","article-title":"Tuning the electronic properties of Fe2(\u03bc-arenedithiolate)(CO)6\u2212n(PMe3)n (n\u2009=\u20090, 2) complexes related to the [Fe\u2013Fe]-hydrogenase active site","volume":"11","year":"2008","journal-title":"C. R. Chim."},{"key":"2025043005592603000_c31","volume-title":"Magnetic Atoms and Molecules","year":"1983"},{"key":"2025043005592603000_c32","doi-asserted-by":"publisher","first-page":"331","DOI":"10.1016\/S0010-8545(00)00326-X","article-title":"Triplets in metal\u2013organic compounds. Chemical tunability of relaxation dynamics","volume":"208","year":"2000","journal-title":"Coord. Chem. Rev."},{"issue":"1-3","key":"2025043005592603000_c33","doi-asserted-by":"publisher","first-page":"53","DOI":"10.1016\/j.cplett.2009.12.042","article-title":"Triplet state properties of a red light emitting [Pt(s-thpy)(acac)] compound","volume":"486","year":"2010","journal-title":"Chem. Phys. Lett."},{"issue":"28","key":"2025043005592603000_c34","doi-asserted-by":"publisher","first-page":"12781","DOI":"10.1021\/jacs.2c03490","article-title":"Excited state magneto-structural correlations related to photoinduced electron spin polarization","volume":"144","year":"2022","journal-title":"J.\u00a0Am. Chem. Soc."},{"key":"2025043005592603000_c35","volume-title":"Angular Momentum: Understanding Spatial Aspects in Chemistry and Physics","year":"1991"},{"key":"2025043005592603000_c36","doi-asserted-by":"publisher","first-page":"2808","DOI":"10.1021\/ja00740a052","article-title":"New highly anisotropic dinitroxide ketone spin label. Sensitive probe for membrane structure","volume":"93","year":"1971","journal-title":"J.\u00a0Am. Chem. Soc."},{"key":"2025043005592603000_c37","doi-asserted-by":"publisher","first-page":"2538","DOI":"10.1021\/ja01067a002","article-title":"Electronic interaction in ketyl radicals","volume":"86","year":"1964","journal-title":"J.\u00a0Am. Chem. Soc."}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0270046\/20504892\/164312_1_5.0270046.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0270046\/20504892\/164312_1_5.0270046.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,4,30]],"date-time":"2025-04-30T09:59:35Z","timestamp":1746007175000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/162\/16\/164312\/3345418\/Excited-triplet-state-zero-field-splitting-in-a"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,4,28]]},"references-count":37,"journal-issue":{"issue":"16","published-print":{"date-parts":[[2025,4,28]]}},"URL":"https:\/\/doi.org\/10.1063\/5.0270046","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"value":"0021-9606","type":"print"},{"value":"1089-7690","type":"electronic"}],"subject":[],"published-other":{"date-parts":[[2025,4,28]]},"published":{"date-parts":[[2025,4,28]]},"article-number":"164312"}}