Formation of Azulene‐Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction
Incorporation of a non‐hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene‐bridged double [6]helicene and heptagon‐containing nanographene by the Scholl reaction, an unexpected azulene‐embedded nanographene and its triflyl...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2020-06, Vol.59 (23), p.9026-9031 |
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| creator | Han, Yi Xue, Zibo Li, Guangwu Gu, Yanwei Ni, Yong Dong, Shaoqiang Chi, Chunyan |
| description | Incorporation of a non‐hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene‐bridged double [6]helicene and heptagon‐containing nanographene by the Scholl reaction, an unexpected azulene‐embedded nanographene and its triflyloxylated product were obtained, as confirmed by X‐ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring‐fused substructure containing two formal azulene units is formed, but only one of them shows an azulene‐like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2‐phenyl migration and a naphthalene to azulene rearrangement reaction according to an in‐silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene‐based molecular materials.
Shifting groups: An unprecedented naphthalene to azulene rearrangement reaction was observed during the Scholl reaction. And an arenium ion mediated 1,2‐phenyl shift also took place. Combined these steps lead to azulene‐embedded nanographene structures having azulene‐like electronic and physical properties. |
| doi_str_mv | 10.1002/anie.201915327 |
| format | Article |
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Shifting groups: An unprecedented naphthalene to azulene rearrangement reaction was observed during the Scholl reaction. And an arenium ion mediated 1,2‐phenyl shift also took place. Combined these steps lead to azulene‐embedded nanographene structures having azulene‐like electronic and physical properties.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201915327</identifier><identifier>PMID: 32096589</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Azulene ; azulenes ; Crystallography ; Electronic properties ; Electronic structure ; Magnetic resonance spectroscopy ; nanostructures ; Naphthalene ; NMR ; NMR spectroscopy ; Nuclear magnetic resonance ; reaction mechanisms ; rearrangements ; Scholl reaction ; Substructures ; Two dimensional analysis</subject><ispartof>Angewandte Chemie International Edition, 2020-06, Vol.59 (23), p.9026-9031</ispartof><rights>2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4767-eb75244ea22ebb7c754cc69ec982aa47bb42267856fb019e69f1c34a28f5e05f3</citedby><cites>FETCH-LOGICAL-c4767-eb75244ea22ebb7c754cc69ec982aa47bb42267856fb019e69f1c34a28f5e05f3</cites><orcidid>0000-0003-4677-3546</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201915327$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201915327$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/32096589$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Han, Yi</creatorcontrib><creatorcontrib>Xue, Zibo</creatorcontrib><creatorcontrib>Li, Guangwu</creatorcontrib><creatorcontrib>Gu, Yanwei</creatorcontrib><creatorcontrib>Ni, Yong</creatorcontrib><creatorcontrib>Dong, Shaoqiang</creatorcontrib><creatorcontrib>Chi, Chunyan</creatorcontrib><title>Formation of Azulene‐Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>Incorporation of a non‐hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene‐bridged double [6]helicene and heptagon‐containing nanographene by the Scholl reaction, an unexpected azulene‐embedded nanographene and its triflyloxylated product were obtained, as confirmed by X‐ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring‐fused substructure containing two formal azulene units is formed, but only one of them shows an azulene‐like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2‐phenyl migration and a naphthalene to azulene rearrangement reaction according to an in‐silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene‐based molecular materials.
Shifting groups: An unprecedented naphthalene to azulene rearrangement reaction was observed during the Scholl reaction. And an arenium ion mediated 1,2‐phenyl shift also took place. Combined these steps lead to azulene‐embedded nanographene structures having azulene‐like electronic and physical properties.</description><subject>Azulene</subject><subject>azulenes</subject><subject>Crystallography</subject><subject>Electronic properties</subject><subject>Electronic structure</subject><subject>Magnetic resonance spectroscopy</subject><subject>nanostructures</subject><subject>Naphthalene</subject><subject>NMR</subject><subject>NMR spectroscopy</subject><subject>Nuclear magnetic resonance</subject><subject>reaction mechanisms</subject><subject>rearrangements</subject><subject>Scholl reaction</subject><subject>Substructures</subject><subject>Two dimensional analysis</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqF0ctO3DAUBmALFXWAdsuyitRNNxl8d9LdiA4XCQ0ShbXleE4mGSX21EmEYMUj8Iw8CY6GoRIbVr59_n05CB0TPCUY0xPjaphSTHIiGFV76IAISlKmFPsS-5yxVGWCTNBh162jzzIsv6IJoziXIssPUHvmQ2v62rvEl8nscWjAwcvT87wtYLmEZbIwzq-C2VRx_nccbaq-MiNKer_zyQ2YEIxbQQuuT_4MoXarpK8g-Wsr3zTjuh3P-Ib2S9N08P2tPUJ3Z_Pb04v06vr88nR2lVqupEqhUIJyDoZSKAplleDWyhxsnlFjuCoKTqmMD5NlEZ8OMi-JZdzQrBSARcmO0K9t7ib4fwN0vW7rzkLTGAd-6DRlkmMuFM4i_fmBrv0QXLydphxLGg3Jo5pulQ2-6wKUehPq1oQHTbAeC6HHQuj3QsQNP95ih6KF5Tvf_XwE-Rbc1w08fBKnZ4vL-f_wV5axlgk</recordid><startdate>20200602</startdate><enddate>20200602</enddate><creator>Han, Yi</creator><creator>Xue, Zibo</creator><creator>Li, Guangwu</creator><creator>Gu, Yanwei</creator><creator>Ni, Yong</creator><creator>Dong, Shaoqiang</creator><creator>Chi, Chunyan</creator><general>Wiley Subscription Services, Inc</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-4677-3546</orcidid></search><sort><creationdate>20200602</creationdate><title>Formation of Azulene‐Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction</title><author>Han, Yi ; Xue, Zibo ; Li, Guangwu ; Gu, Yanwei ; Ni, Yong ; Dong, Shaoqiang ; Chi, Chunyan</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4767-eb75244ea22ebb7c754cc69ec982aa47bb42267856fb019e69f1c34a28f5e05f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Azulene</topic><topic>azulenes</topic><topic>Crystallography</topic><topic>Electronic properties</topic><topic>Electronic structure</topic><topic>Magnetic resonance spectroscopy</topic><topic>nanostructures</topic><topic>Naphthalene</topic><topic>NMR</topic><topic>NMR spectroscopy</topic><topic>Nuclear magnetic resonance</topic><topic>reaction mechanisms</topic><topic>rearrangements</topic><topic>Scholl reaction</topic><topic>Substructures</topic><topic>Two dimensional analysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Han, Yi</creatorcontrib><creatorcontrib>Xue, Zibo</creatorcontrib><creatorcontrib>Li, Guangwu</creatorcontrib><creatorcontrib>Gu, Yanwei</creatorcontrib><creatorcontrib>Ni, Yong</creatorcontrib><creatorcontrib>Dong, Shaoqiang</creatorcontrib><creatorcontrib>Chi, Chunyan</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Han, Yi</au><au>Xue, Zibo</au><au>Li, Guangwu</au><au>Gu, Yanwei</au><au>Ni, Yong</au><au>Dong, Shaoqiang</au><au>Chi, Chunyan</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Formation of Azulene‐Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2020-06-02</date><risdate>2020</risdate><volume>59</volume><issue>23</issue><spage>9026</spage><epage>9031</epage><pages>9026-9031</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>Incorporation of a non‐hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene‐bridged double [6]helicene and heptagon‐containing nanographene by the Scholl reaction, an unexpected azulene‐embedded nanographene and its triflyloxylated product were obtained, as confirmed by X‐ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring‐fused substructure containing two formal azulene units is formed, but only one of them shows an azulene‐like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2‐phenyl migration and a naphthalene to azulene rearrangement reaction according to an in‐silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene‐based molecular materials.
Shifting groups: An unprecedented naphthalene to azulene rearrangement reaction was observed during the Scholl reaction. And an arenium ion mediated 1,2‐phenyl shift also took place. Combined these steps lead to azulene‐embedded nanographene structures having azulene‐like electronic and physical properties.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>32096589</pmid><doi>10.1002/anie.201915327</doi><tpages>6</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0003-4677-3546</orcidid></addata></record> |
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| subjects | Azulene azulenes Crystallography Electronic properties Electronic structure Magnetic resonance spectroscopy nanostructures Naphthalene NMR NMR spectroscopy Nuclear magnetic resonance reaction mechanisms rearrangements Scholl reaction Substructures Two dimensional analysis |
| title | Formation of Azulene‐Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction |
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