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Specifically, oxidation with [bis(trifluoroacetoxy)iodo]benzene (PIFA) gave closed\u2010[7]helicene dimers connected at the \u03b2\u2010position of one of the pyrrole units with remarkably elongated C\u2212C bonds of about 1.60\u2005\u00c5. Although this bond was intact against thermal and physical activations, homolytic bond dissociation took place in DMSO upon irradiation with UV light to give the corresponding monomers. Thus, interconversion between the closed\u2010helicene monomer and dimer was achieved. The optically pure dimer was photo\u2010dissociated into the monomers associated with a turn\u2010on of circularly polarized luminescence (CPL).<\/jats:p>","DOI":"10.1002\/anie.202314968","type":"journal-article","created":{"date-parts":[[2023,10,26]],"date-time":"2023-10-26T16:23:44Z","timestamp":1698337424000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Synthesis of Closed\u2010Heterohelicenes Interconvertible between Their Monomeric and Dimeric Forms"],"prefix":"10.1002","volume":"62","author":[{"given":"Yusuke","family":"Matsuo","sequence":"first","affiliation":[{"name":"Department of Chemistry Graduate School of Science Kyoto University  Sakyo-ku Kyoto 606-8502 Japan"},{"name":"Department of Molecular Engineering Graduate School of Engineering Kyoto University  Nishikyo-ku Kyoto 615-8510 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hetero[n]circulenes;"},{"key":"e_1_2_7_67_2","first-page":"498","volume":"27","author":"Hensel T.","year":"2016","journal-title":"Synlett"},{"key":"e_1_2_7_68_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CC06495E"},{"key":"e_1_2_7_69_2","doi-asserted-by":"publisher","DOI":"10.3987\/REV-22-982"},{"key":"e_1_2_7_70_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202116789"},{"key":"e_1_2_7_71_1","first-page":"147","volume":"51","author":"Matsuo Y.","year":"2022","journal-title":"Synthesis"},{"key":"e_1_2_7_72_1","unstructured":"Deposition numbers2205273 (for3S2N) 2205276 (forSN\u2032SN\u2032-S) 2205277 (for(SNSN-S)2) 2205272 (for2S3N) 2205275 (forSN\u2032N\u2032N\u2032-S) and 2205274 (for(SNNN-S)2)contain 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_73_1","unstructured":"These pitches are longer than those of calculated structures without the diphenylthiophene linker. This implies that the presence of the linker indeed increases the strain energy. See Figure\u2005S7\u201314 (for monomer) and Figure\u2005S7\u201315 (for dimer) in the Supporting Information."},{"key":"e_1_2_7_74_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201800617"},{"key":"e_1_2_7_75_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9SC05087F"},{"key":"e_1_2_7_76_1","unstructured":"Because(SNSN-S)2has two chiral sp3carbon atoms the chirality definitions of (R R) for (P P)-(SNSN-S)2and (S S) for (M M)-(SNSN-S)2based on the Cahn-Ingold-Prelog rule can also be adopted."},{"key":"e_1_2_7_77_1","unstructured":"\u00a0"},{"key":"e_1_2_7_78_2","doi-asserted-by":"publisher","DOI":"10.1039\/C8OB00343B"},{"key":"e_1_2_7_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c01852"},{"key":"e_1_2_7_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c01106"},{"key":"e_1_2_7_81_1","unstructured":"Instead of the addition of NaBH4\/MeOH the reaction can be quenched by passing through an alumina column to afford the product in a similar yield."},{"key":"e_1_2_7_82_1","unstructured":"NCIPLOT4;"},{"key":"e_1_2_7_83_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.0c00063"},{"key":"e_1_2_7_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/ct100641a"},{"key":"e_1_2_7_85_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja100936w"},{"key":"e_1_2_7_86_1","doi-asserted-by":"publisher","DOI":"10.1002\/ajoc.201900168"},{"key":"e_1_2_7_87_1","unstructured":"The aromaticity of the amine-type and imine-type pyrrole segments has been evaluated by NICS(0) and HOMA calculations (Figure\u2005S7\u201311)."},{"key":"e_1_2_7_88_1","unstructured":"In this photoreaction monomerSNSN-Sis thought to be obtained via disproportion reaction of the intermediate radical species. The corresponding diradical species generated by the disproportion reaction is hydrogenated with trace amount of water in the solvent to produceSNSN-S(Figure\u2005S7\u201317). This plausible reaction mechanism is consistent with the experimental result that\u03b2-deuterium-labeled monomer was not obtained in the photoreaction in DMSO-d6in the presence of D2O (Figure\u2005S3\u201324)."},{"key":"e_1_2_7_89_1","unstructured":"Detailed measurement conditions: The compound(SNSN-S)2was dissolved in THF with a concentration of 6.2\u00d710\u22126\u2005M and loaded in a normal 1\u2005cm quartz cell. Photoexcitation was carried out with continuous Hg\u2212Xe-lamp (LC8\u2005L9566 Hamamatsu Photonics) collimated by a lens and an iris to a diameter of ca. 5\u2005mm. Only 365 nm i-line was passed through a bandpass filter and optical power was adjusted to be 600 uW. Emission spectra were simultaneously monitored by a combination of a lens an optical fiber spectrograph and EMCCD camera (Andor Kymera 328i and Newton 970P) with the orthogonal configuration of excitation and emission path."},{"key":"e_1_2_7_90_1","unstructured":"Without bridging units the racemization activation energies are expected to be reduced (+31.7\u2005kcal\/mol forSNSN-Swithout a linker and +24.5\u2005kcal\/mol forSNNN-Swithout a linker) indicating the importance of closed-helicene-type structure (Figure\u2005S9\u20134 S9\u20135)."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202314968","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,7,25]],"date-time":"2024-07-25T11:40:58Z","timestamp":1721907658000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202314968"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,11,9]]},"references-count":90,"journal-issue":{"issue":"50","published-print":{"date-parts":[[2023,12,11]]}},"alternative-id":["10.1002\/anie.202314968"],"URL":"https:\/\/doi.org\/10.1002\/anie.202314968","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,11,9]]},"assertion":[{"value":"2023-10-05","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-11-09","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202314968"}}