{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T16:24:12Z","timestamp":1790612652941,"version":"4.1.0"},"reference-count":29,"publisher":"National Academy of Sciences","issue":"14","license":[{"start":{"date-parts":[[2024,3,27]],"date-time":"2024-03-27T00:00:00Z","timestamp":1711497600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE-2154210"],"award-info":[{"award-number":["CHE-2154210"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2024,4,2]]},"abstract":"<jats:p>\n                    Photochemical valence bond isomerization of a crystalline Dewar benzene (\n                    <jats:bold>DB<\/jats:bold>\n                    ) diacid monoanion salt with an acetophenone-linked piperazinium cation that serves as an intramolecular triplet energy sensitizer (\n                    <jats:bold>DB-AcPh-Pz<\/jats:bold>\n                    ) exhibits a quantum chain reaction with as many as 450 product molecules per photon absorbed (\u03a6 \u2248 450). By contrast, isomorphous crystals of the\n                    <jats:bold>DB<\/jats:bold>\n                    diacid monosalt of an ethylbenzene-linked piperazinium (\n                    <jats:bold>DB-EtPh-Pz<\/jats:bold>\n                    ) lacking a triplet sensitizer showed a less impressive quantum yield of ca. \u03a6 \u2248 22. To establish the critical importance of a triplet excited state carrier in the adiabatic photochemical reaction we prepared mixed crystals with\n                    <jats:bold>DB-AcPh-Pz<\/jats:bold>\n                    as a dilute triplet sensitizer guest in crystals of\n                    <jats:bold>DB-EtPh-Pz<\/jats:bold>\n                    . As expected from their high structural similarities, solid solutions were easily formed with the triplet sensitizer salt in the range of 0.1 to 10%. Experiments carried out under conditions where light is absorbed by the triplet sensitizer-linked\n                    <jats:bold>DB-AcPh-Pz<\/jats:bold>\n                    can be used to initiate a triplet state adiabatic reaction from\n                    <jats:bold>\n                      <jats:sup>3<\/jats:sup>\n                      DB-AcPh-Pz\n                    <\/jats:bold>\n                    to\n                    <jats:bold>\n                      <jats:sup>3<\/jats:sup>\n                      HB*-AcPh-Pz\n                    <\/jats:bold>\n                    , which can serve as a chain carrier and transfer energy to an unreacted\n                    <jats:bold>DB-EtPh-Pz<\/jats:bold>\n                    where exciton delocalization in the crystalline solid solution can help carry out an efficient energy transfer and enable a quantum chain employing the photoproduct as a triplet chain carrier. Excitation of mixed crystals with as little as 0.1% triplet sensitizer resulted in an extraordinarily high quantum yield \u03a6 \u2248 517.\n                  <\/jats:p>","DOI":"10.1073\/pnas.2401982121","type":"journal-article","created":{"date-parts":[[2024,3,27]],"date-time":"2024-03-27T13:04:03Z","timestamp":1711544643000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":6,"title":["Reaction amplification with a gain: Triplet exciton\u2013mediated quantum chain using mixed crystals with a tailor-made triplet sensitizer"],"prefix":"10.1073","volume":"121","author":[{"given":"Indrajit","family":"Paul","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90024-1569"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Krzysztof A.","family":"Konieczny","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90024-1569"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Roberto","family":"Chavez","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90024-1569"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6268-1943","authenticated-orcid":false,"given":"Miguel A.","family":"Garcia-Garibay","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90024-1569"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"341","published-online":{"date-parts":[[2024,3,27]]},"reference":[{"key":"e_1_3_4_1_2","doi-asserted-by":"publisher","DOI":"10.1038\/natrevmats.2017.63"},{"key":"e_1_3_4_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1232994"},{"key":"e_1_3_4_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja075014k"},{"key":"e_1_3_4_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00257G"},{"key":"e_1_3_4_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja078301x"},{"key":"e_1_3_4_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma050348k"},{"key":"e_1_3_4_7_2","first-page":"91","article-title":"Mechanisms of photochemical reactions in solution. LX. Photochemical isomerization of 2,4-hexadiene via a quantum-chain mechanism","author":"Hyndman H. L.","year":"1969","unstructured":"The first documented quantum chain reaction involves the triplet sensitized photoisomerization of 2,4-hexadiene: H. L. Hyndman, B. M. Monroe, G. S. Hammond, Mechanisms of photochemical reactions in solution. LX. Photochemical isomerization of 2,4-hexadiene via a quantum-chain mechanism. J. Am. Chem. Soc. 91, 2852\u20132859 (1969).","journal-title":"J. Am. Chem. Soc."},{"key":"e_1_3_4_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00799a025"},{"key":"e_1_3_4_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1010-6030(00)00419-6"},{"key":"e_1_3_4_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)75296-8"},{"key":"e_1_3_4_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1010-6030(98)00409-2"},{"key":"e_1_3_4_12_2","first-page":"363","article-title":"Energy storage and release direct and sensitized photoreactions of Dewar benzene and prismane","volume":"1","author":"Turro N. J.","year":"1977","unstructured":"N. J. Turro, V. Ramamurthy, T. H. J. Katz, Energy storage and release direct and sensitized photoreactions of Dewar benzene and prismane. Nouv. J. Chim. 1, 363 (1977).","journal-title":"Nouv. J. 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