{"_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"}, "item_10_biblio_info_6": {"attribute_name": "\u66f8\u8a8c\u60c5\u5831", "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"}]}]}, "item_10_description_4": {"attribute_name": "\u6284\u9332", "attribute_value_mlt": [{"subitem_description": "The reversible formation of \u03c3-bonds between organic radicals has been widely investigated. However, reports on the formation of \u03c3-dimers from delocalized \u03c0-radical cations are scarce. Herein, we report the reversible \u03c3-dimerization behavior of a bowl-shaped \u03c0-radical cation generated from a nitrogen-embedded buckybowl, both in the crystalline state and in solution. The detailed structure of the \u03c3-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\u2013carbon \u03c3-bond formation upon reducing the temperature. 1H NMR and optical spectroscopy measurements confirmed the formation of a \u03c3-dimer at low temperature. Comparative studies with a similar yet planar \u03c0-conjugated system suggested that the curved structure of the bowl-shaped \u03c0-radical cation facilitates the \u03c3-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 \u03c0-radical cations. The methoxylation reaction proceeded only for the curved \u03c0-radical cation. Theoretical calculations revealed that the large relief of structural strain at the \u03b1-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_type": "Abstract"}]}, "item_10_description_5": {"attribute_name": "\u5185\u5bb9\u8a18\u8ff0", "attribute_value_mlt": [{"subitem_description": "\u30d5\u30a1\u30a4\u30eb\u516c\u958b\uff1a2019/04/04", "subitem_description_type": "Other"}]}, "item_10_publisher_32": {"attribute_name": "\u51fa\u7248\u8005", "attribute_value_mlt": [{"subitem_publisher": "ACS Publications"}]}, "item_10_relation_11": {"attribute_name": "DOI", "attribute_value_mlt": [{"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": "\u6a29\u5229", "attribute_value_mlt": [{"subitem_rights": "\u201cThis document is the Accepted Manuscript version of a Published Work that appeared in final form in [Journal of the American Chemical Society], copyright \u00a9 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].\u201d "}]}, "item_10_select_15": {"attribute_name": "\u8457\u8005\u7248\u30d5\u30e9\u30b0", "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": "ISSN"}]}, "item_creator": {"attribute_name": "\u8457\u8005", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "Yokoi, Hiroki"}], "nameIdentifiers": [{"nameIdentifier": "78619", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Hiroto, Satoru"}], "nameIdentifiers": [{"nameIdentifier": "78620", "nameIdentifierScheme": "WEKO"}]}, {"creatorNames": [{"creatorName": "Shinokubo, Hiroshi"}], "nameIdentifiers": [{"nameIdentifier": "78621", "nameIdentifierScheme": "WEKO"}]}]}, "item_files": {"attribute_name": "\u30d5\u30a1\u30a4\u30eb\u60c5\u5831", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2019-04-04"}], "displaytype": "detail", "download_preview_message": "", "file_order": 0, "filename": "JACS180312.pdf", "filesize": [{"value": "5.9 MB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_free", "mimetype": "application/pdf", "size": 5900000.0, "url": {"label": "JACS180312", "url": "https://nagoya.repo.nii.ac.jp/record/26217/files/JACS180312.pdf"}, "version_id": "ff4c9a0d-5e78-4a61-ada1-e38f81fd6e56"}]}, "item_language": {"attribute_name": "\u8a00\u8a9e", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "item_resource_type": {"attribute_name": "\u8cc7\u6e90\u30bf\u30a4\u30d7", "attribute_value_mlt": [{"resourcetype": "journal article", "resourceuri": "http://purl.org/coar/resource_type/c_6501"}]}, "item_title": "Reversible \u03c3-Bond Formation in Bowl-Shaped \u03c0-Radical Cations: The Effects of Curved and Planar Structures", "item_titles": {"attribute_name": "\u30bf\u30a4\u30c8\u30eb", "attribute_value_mlt": [{"subitem_title": "Reversible \u03c3-Bond Formation in Bowl-Shaped \u03c0-Radical Cations: The Effects of Curved and Planar Structures"}]}, "item_type_id": "10", "owner": "1", "path": ["320/321/322"], "permalink_uri": "http://hdl.handle.net/2237/00028421", "pubdate": {"attribute_name": "\u516c\u958b\u65e5", "attribute_value": "2018-08-06"}, "publish_date": "2018-08-06", "publish_status": "0", "recid": "26217", "relation": {}, "relation_version_is_last": true, "title": ["Reversible \u03c3-Bond Formation in Bowl-Shaped \u03c0-Radical Cations: The Effects of Curved and Planar Structures"], "weko_shared_id": null}