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However, a large disparity in the distribution of the excitonic center of mass, singlet\u2010triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy\u2010coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin\u2010orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution\u2010stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super\u2010exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency (<jats:italic>k<\/jats:italic><jats:sub>ISC<\/jats:sub>) but <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/anie202305323-math-0001.png\" xlink:title=\"urn:x-wiley:14337851:media:anie202305323:anie202305323-math-0001\"\/>\n form triplets in MOF in contrast to the frameworks that are built from linkers with sizable <jats:italic>k<\/jats:italic><jats:sub>ISC<\/jats:sub> but <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/anie202305323-math-0002.png\" xlink:title=\"urn:x-wiley:14337851:media:anie202305323:anie202305323-math-0002\"\/>\n. This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes.<\/jats:p>","DOI":"10.1002\/anie.202305323","type":"journal-article","created":{"date-parts":[[2023,8,1]],"date-time":"2023-08-01T01:58:51Z","timestamp":1690855131000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Triplet Generation Through Singlet Fission in Metal\u2010Organic Framework: An Alternative Route to Inefficient Singlet\u2010Triplet Intersystem Crossing"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7318-466X","authenticated-orcid":false,"given":"Sreehari","family":"Surendran Rajasree","sequence":"first","affiliation":[{"name":"School of Chemical and Biomolecular Sciences Southern Illinois University Carbondale  1245 Lincoln Dr. 62901 Carbondale IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8422-3583","authenticated-orcid":false,"given":"Jierui","family":"Yu","sequence":"additional","affiliation":[{"name":"School of Chemical and Biomolecular Sciences Southern Illinois University Carbondale  1245 Lincoln Dr. 62901 Carbondale IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8343-5189","authenticated-orcid":false,"given":"H. Christopher","family":"Fry","sequence":"additional","affiliation":[{"name":"Center for Nanoscale Materials Argonne National Laboratory  9700 S Cass Ave 60439 Lemont IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryther","family":"Anderson","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biological Engineering Colorado School of Mines  1500 Illinois St 80401 Golden CO USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4815-6253","authenticated-orcid":false,"given":"Wenqian","family":"Xu","sequence":"additional","affiliation":[{"name":"X-ray Science Division Advanced Photon Source Argonne National Laboratory  9700 S Cass Ave 60439 Lemont IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-2107-0225","authenticated-orcid":false,"given":"Riya","family":"Krishnan","sequence":"additional","affiliation":[{"name":"School of Chemical and Biomolecular Sciences Southern Illinois University Carbondale  1245 Lincoln Dr. 62901 Carbondale IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3252-7870","authenticated-orcid":false,"given":"Jiaxin","family":"Duan","sequence":"additional","affiliation":[{"name":"Department of Chemistry Northwestern University  2145 Sheridan Road 60208 Evanston IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8462-9054","authenticated-orcid":false,"given":"Subhadip","family":"Goswami","sequence":"additional","affiliation":[{"name":"Department of Chemistry Northwestern University  2145 Sheridan Road 60208 Evanston IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3237-0199","authenticated-orcid":false,"given":"Diego","family":"A. G\u00f3mez\u2010Gualdr\u00f3n","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biological Engineering Colorado School of Mines  1500 Illinois St 80401 Golden CO USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7998-4492","authenticated-orcid":false,"given":"Pravas","family":"Deria","sequence":"additional","affiliation":[{"name":"School of Chemical and Biomolecular Sciences Southern Illinois University Carbondale  1245 Lincoln Dr. 62901 Carbondale IL USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,8,8]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC01047E"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4QI00053F"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0427101"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2020.07.010"},{"key":"e_1_2_7_6_1","unstructured":"\u00a0"},{"key":"e_1_2_7_7_2","volume-title":"Modern Molecular Photochemistry","author":"Turro N. 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Alternatively these energies can be obtained from TDDFT computations:andfor H4TBAPy are 2.96 and 1.79\u2005eV; for NU-1000 are 2.91 and 1.61\u2005eV; for H4PEPF are 3.20 and 2.07\u2005eV; and for SIU-100 are 3.31 and 2.09\u2005eV."},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b07498"},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41563-022-01368-1"},{"key":"e_1_2_7_59_1","unstructured":"In terms of triplet quenching but may involve photo-induced electron transfer producing oxygen radical anion."},{"key":"e_1_2_7_60_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b02188"},{"key":"e_1_2_7_61_1","unstructured":"\u00a0"},{"key":"e_1_2_7_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b01613"},{"key":"e_1_2_7_63_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC01893F"},{"key":"e_1_2_7_64_1","unstructured":"Deposition number2216519 (for SIU-175)contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_7_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5b08860"},{"key":"e_1_2_7_66_1","unstructured":"Solvent-accessible porosity was probed via thermogravimetric analysis (TGA) of the respective DMF-filled MOF sample showing an initial mass loss of \u224887\u2009% associated with the evaporation of the solvent filled within the MOF pores; (see Supporting Information sec C3)."},{"key":"e_1_2_7_67_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2ra21100a"},{"key":"e_1_2_7_68_1","unstructured":"\u00a0"},{"key":"e_1_2_7_69_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3cc48562e"},{"key":"e_1_2_7_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja408959g"},{"key":"e_1_2_7_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b13211"},{"key":"e_1_2_7_72_1","unstructured":"Formed from higher energy singlets at the early time (<1\u2005ns) and appears at the same proportion as found in pristine MOF and were not quenched by atRA or O2; this signal is associated with low-energy \u201ctrapped\u201d state formed at the imperfection sites of the crystals."},{"key":"e_1_2_7_73_1","unstructured":"Emission from the initial S1S0pair appearsca525\u2005nm; alternatively the Sl\u2192S0emission appears at \u2248580\u2005nm and at a longer time delay. Considering the fast timescale for this SF-mediated formation of1(TT) state an alternate possibility can be considered where the population is condensed to a specific\/selective vibrational state. For that case however the spontaneous emission envelope would be narrow and centered around 550\u2005nm and would not show the time-resolved profile described in Figure\u2005. Condensing the S1\u2013S0transition probability to one of the vibrational levels of the S0 state that is not spontaneous will be very unusual."},{"key":"e_1_2_7_74_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.0c07920"},{"key":"e_1_2_7_75_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.7b02697"},{"key":"e_1_2_7_76_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4794427"},{"key":"e_1_2_7_77_1","unstructured":"\u00a0"},{"key":"e_1_2_7_78_2","doi-asserted-by":"publisher","DOI":"10.1039\/b506575e"},{"key":"e_1_2_7_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/jz900170m"},{"key":"e_1_2_7_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.9b03079"},{"key":"e_1_2_7_81_1","unstructured":"This resolved spectrum is caused due to a diminished 580\u2005nm peak that was highly intense in the unmodified SIU-175 (caused via reverse populated via TTA) and somewhat quenched possibly via energy transfer to TPP(Pd) whose absorption band spans from 520\u2013600\u2005nm."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1002\/anie.202305323","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202305323","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,9,14]],"date-time":"2023-09-14T16:53:15Z","timestamp":1694710395000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202305323"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,8,8]]},"references-count":81,"journal-issue":{"issue":"38","published-print":{"date-parts":[[2023,9,18]]}},"alternative-id":["10.1002\/anie.202305323"],"URL":"https:\/\/doi.org\/10.1002\/anie.202305323","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,8,8]]},"assertion":[{"value":"2023-04-18","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-08-08","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202305323"}}