{"created":"2021-03-01T06:34:07.378577+00:00","id":26217,"links":{},"metadata":{"_buckets":{"deposit":"94772cd8-7dce-4e48-b807-23c1527be8d0"},"_deposit":{"id":"26217","owners":[],"pid":{"revision_id":0,"type":"depid","value":"26217"},"status":"published"},"_oai":{"id":"oai:nagoya.repo.nii.ac.jp:00026217","sets":["320:321:322"]},"author_link":["78619","78620","78621"],"item_10_biblio_info_6":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"2018-04-04","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"13","bibliographicPageEnd":"4655","bibliographicPageStart":"4649","bibliographicVolumeNumber":"140","bibliographic_titles":[{"bibliographic_title":"Journal of the American Chemical Society","bibliographic_titleLang":"en"}]}]},"item_10_description_4":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"The reversible formation of σ-bonds between organic radicals has been widely investigated. However, reports on the formation of σ-dimers from delocalized π-radical cations are scarce. Herein, we report the reversible σ-dimerization behavior of a bowl-shaped π-radical cation generated from a nitrogen-embedded buckybowl, both in the crystalline state and in solution. The detailed structure of the σ-dimer in the crystalline state was determined by a single-crystal X-ray diffraction analysis. The monomeric radical cation exists predominantly in solution at room temperature, while dimerization of the radical cations occurs through carbon–carbon σ-bond formation upon reducing the temperature. 1H NMR and optical spectroscopy measurements confirmed the formation of a σ-dimer at low temperature. Comparative studies with a similar yet planar π-conjugated system suggested that the curved structure of the bowl-shaped π-radical cation facilitates the σ-dimerization at one of the internal sp^2-hybridized carbon atoms. This trend was also observed for the nucleophilic addition reaction of methanol to the π-radical cations. The methoxylation reaction proceeded only for the curved π-radical cation. Theoretical calculations revealed that the large relief of structural strain at the α-carbon atom during the dimerization or nucleophilic addition reactions accelerated the bond formation at the internal carbon atom of the curved radical cation.","subitem_description_language":"en","subitem_description_type":"Abstract"}]},"item_10_description_5":{"attribute_name":"内容記述","attribute_value_mlt":[{"subitem_description":"ファイル公開：2019/04/04","subitem_description_language":"ja","subitem_description_type":"Other"}]},"item_10_publisher_32":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"ACS Publications","subitem_publisher_language":"en"}]},"item_10_relation_11":{"attribute_name":"DOI","attribute_value_mlt":[{"subitem_relation_type":"isVersionOf","subitem_relation_type_id":{"subitem_relation_type_id_text":"https://doi.org/10.1021/jacs.8b00798","subitem_relation_type_select":"DOI"}}]},"item_10_rights_12":{"attribute_name":"権利","attribute_value_mlt":[{"subitem_rights":"“This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Journal of the American Chemical Society], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [http://pubs.acs.org/articlesonrequest/AOR-NfW9REWxjIetX62GFwqd].” ","subitem_rights_language":"en"}]},"item_10_select_15":{"attribute_name":"著者版フラグ","attribute_value_mlt":[{"subitem_select_item":"author"}]},"item_10_source_id_7":{"attribute_name":"ISSN","attribute_value_mlt":[{"subitem_source_identifier":"0002-7863","subitem_source_identifier_type":"PISSN"}]},"item_1615787544753":{"attribute_name":"出版タイプ","attribute_value_mlt":[{"subitem_version_resource":"http://purl.org/coar/version/c_ab4af688f83e57aa","subitem_version_type":"AM"}]},"item_access_right":{"attribute_name":"アクセス権","attribute_value_mlt":[{"subitem_access_right":"open access","subitem_access_right_uri":"http://purl.org/coar/access_right/c_abf2"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"Yokoi, Hiroki","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"78619","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"Hiroto, Satoru","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"78620","nameIdentifierScheme":"WEKO"}]},{"creatorNames":[{"creatorName":"Shinokubo, Hiroshi","creatorNameLang":"en"}],"nameIdentifiers":[{"nameIdentifier":"78621","nameIdentifierScheme":"WEKO"}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2019-04-04"}],"displaytype":"detail","filename":"JACS180312.pdf","filesize":[{"value":"5.9 MB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"JACS180312","objectType":"fulltext","url":"https://nagoya.repo.nii.ac.jp/record/26217/files/JACS180312.pdf"},"version_id":"ff4c9a0d-5e78-4a61-ada1-e38f81fd6e56"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"journal article","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"Reversible σ-Bond Formation in Bowl-Shaped π-Radical Cations: The Effects of Curved and Planar Structures","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"Reversible σ-Bond Formation in Bowl-Shaped π-Radical Cations: The Effects of Curved and Planar Structures","subitem_title_language":"en"}]},"item_type_id":"10","owner":"1","path":["322"],"pubdate":{"attribute_name":"PubDate","attribute_value":"2018-08-06"},"publish_date":"2018-08-06","publish_status":"0","recid":"26217","relation_version_is_last":true,"title":["Reversible σ-Bond Formation in Bowl-Shaped π-Radical Cations: The Effects of Curved and Planar Structures"],"weko_creator_id":"1","weko_shared_id":-1},"updated":"2023-01-16T04:16:45.484545+00:00"}