{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,28]],"date-time":"2026-08-28T07:19:15Z","timestamp":1787901555922,"version":"build-2784847793"},"reference-count":51,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T00:00:00Z","timestamp":1787356800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T00:00:00Z","timestamp":1787356800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["364549901"],"award-info":[{"award-number":["364549901"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemSusChem"],"published-print":{"date-parts":[[2026,8,27]]},"abstract":"<jats:p>\n                    Thermally activated delayed fluorescence (TADF) compounds have found great application as photocatalysts in recent years. Their use as photosensitizers (PS), however, is still limited although they have huge potential as abundant alternatives to traditional noble metal\u2010based PSs, such as [Ru(bpy)\n                    <jats:sub>3<\/jats:sub>\n                    ]\n                    <jats:sup>2+<\/jats:sup>\n                    . We herein investigate the TADF compound 2,4,5,6\u2010tetra(9\n                    <jats:italic>H<\/jats:italic>\n                    \u2010carbazol\u20109\u2010yl)isophthalonitrile\u00a0(4CzIPN) as a PS together with the catalyst cobaloxime (Co(dmgH)\n                    <jats:sub>2<\/jats:sub>\n                    (py)Cl) in the photochemical hydrogen evolution reaction (HER). Systematic optimization of the solvent composition, 4CzIPN and catalyst concentration, and sacrificial electron donor (SED) identified ammonium ascorbate as the most effective SED under the conditions tested. Under optimized conditions, the system reached a TON of 6451\u2009\u00b1\u200982 after 20\u2009h irradiation. Stern\u2013Volmer quenching experiments and scalar\u2010relativistic quantum\u2010chemical calculations provided rate constants for the different processes in the photosensitization mechanism, demonstrating that the quenching of the excited singlet state (S\n                    <jats:sub>1<\/jats:sub>\n                    ) of 4CzIPN by ammonium ascorbate is by far more dominant than the quenching of its excited triplet state (T\n                    <jats:sub>1<\/jats:sub>\n                    ). This work demonstrates that 4CzIPN can sensitize the cobaloxime\u2010catalyzed light\u2010driven HER with ammonium ascorbate as the SED and provides mechanistic insight into the role of singlet\u2010 and triplet\u2010state quenching in TADF photosensitization.\n                  <\/jats:p>","DOI":"10.1002\/cssc.70942","type":"journal-article","created":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T11:11:35Z","timestamp":1787397095000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["4CzIPN Photosensitizes the Cobaloxime\u2010Catalyzed Light\u2010Driven Hydrogen Evolution Reaction"],"prefix":"10.1002","volume":"19","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-1955-8151","authenticated-orcid":false,"given":"Alexander","family":"Tombrink","sequence":"first","affiliation":[{"name":"Institute of Organic Chemistry II and Advanced Materials Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Benedikt","family":"Callies","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Macromolecular Chemistry Friedrich Schiller University Jena  Jena Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6428-7528","authenticated-orcid":false,"given":"Stephan","family":"Kupfer","sequence":"additional","affiliation":[{"name":"Institute of Physical Chemistry Friedrich Schiller University Jena  Jena Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3603-5980","authenticated-orcid":false,"given":"Daniel","family":"Kowalcyk","sequence":"additional","affiliation":[{"name":"Institute of Chemical Engineering Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-9297-4547","authenticated-orcid":false,"given":"Benedikt","family":"Wiedemann","sequence":"additional","affiliation":[{"name":"Institute of Chemical Engineering Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6104-4953","authenticated-orcid":false,"given":"Dirk","family":"Ziegenbalg","sequence":"additional","affiliation":[{"name":"Institute of Chemical Engineering Ulm University  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5578-3266","authenticated-orcid":false,"given":"Kalina","family":"Peneva","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry and Macromolecular Chemistry Friedrich Schiller University Jena  Jena Germany"},{"name":"Center for Energy and Environmental Chemistry Jena (CEEC Jena)  Jena Germany"},{"name":"Jena Center for Soft Matter (JCSM) Friedrich Schiller University Jena  Jena Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2430-1380","authenticated-orcid":false,"given":"Birgit","family":"Esser","sequence":"additional","affiliation":[{"name":"Institute of Organic Chemistry II and Advanced Materials Ulm University  Ulm Germany"},{"name":"CELEST Green Energy Lab Ulm Ulm University  Ulm Germany"},{"name":"Electrochemical Energy Storage Helmholtz Institute Ulm (HIU)  Ulm Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,8,22]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202305730"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2007.08.014"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/er.3549"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.2c00460"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC03103H"},{"key":"e_1_2_8_7_1","first-page":"271","article-title":"Efficient Homogeneous Photochemical Hydrogen Generation and Water Reduction Mediated by Cobaloxime or Macrocyclic Cobalt Complexes","volume":"14","author":"Hawecker J.","year":"1983","journal-title":"Nouveau Journal De Chimie"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3TA04450E"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja1057357"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c08171"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.3c00755"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00198A"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC04593H"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b08933"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.catcom.2018.09.018"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202500247"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC01047E"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.crci.2015.11.026"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.7b04000"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/D6EY00029K"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja804650g"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3RE00398A"},{"key":"e_1_2_8_23_1","first-page":"e01504","article-title":"Unlocking Spin Dynamics: Spin\u2010Orbit Coupling Driven Spin State Interconversion in Carbazole\u2010Containing TADF Emitters","volume":"2","author":"Morgenstern A.","year":"2025","journal-title":"Advanced Optical Materials"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/open.201900141"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.orgel.2016.11.035"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-46406-5"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/b508541a"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.478522"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.1c12138"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201301860"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic400490y"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature11687"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3SE00546A"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic900389z"},{"key":"e_1_2_8_35_1","first-page":"0935","article-title":"Photocatalytic Semi\u2010Hydrogenation of Acetylene to Polymer\u2010Grade Ethylene With Molecular and Metal\u2013Organic Framework Cobaloximes","volume":"37","author":"Stone A. E.","year":"2014","journal-title":"Advanced Materials"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2011.05.015"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC05047D"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar900253e"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00086A"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.macromol.0c00474"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c01201"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.2c18529"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja903044n"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.4c02609"},{"key":"e_1_2_8_45_1","volume-title":"Principles of Fluorescence Spectroscopy","author":"Lakowicz J. R.","year":"2010"},{"key":"e_1_2_8_46_1","volume-title":"Modern Molecular Photochemistry","author":"Turro N. J.","year":"1991"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp404120s"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4SC00033A"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5RA00157A"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/ajoc.202500256"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5SC04948B"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c10614"}],"container-title":["ChemSusChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cssc.70942","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/cssc.70942","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cssc.70942","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,28]],"date-time":"2026-08-28T06:56:22Z","timestamp":1787900182000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cssc.70942"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,22]]},"references-count":51,"journal-issue":{"issue":"16","published-print":{"date-parts":[[2026,8,27]]}},"alternative-id":["10.1002\/cssc.70942"],"URL":"https:\/\/doi.org\/10.1002\/cssc.70942","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv-2026-fl6jw\/v2","asserted-by":"object"}]},"ISSN":["1864-5631","1864-564X"],"issn-type":[{"value":"1864-5631","type":"print"},{"value":"1864-564X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,22]]},"assertion":[{"value":"2026-01-22","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-07-17","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-08-22","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e70942"}}