Conjugation between 3D and 2D aromaticity: does it really exist? The case of carborane-fused heterocycles
Although several synthesized icosahedral carborane fused 2D π-ring systems are known, and even considerable conjugation has been noted between them in some cases, the phenomenon itself is not fully understood. Based on the results of our computational study, it can be concluded that the 2D aromatic...
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| Veröffentlicht in: | Chemical science (Cambridge) 2022-10, Vol.13 (38), p.11388-11393 |
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| creator | Buzsáki, Dániel Kovács, Máté Barnabás Hümpfner, Evelyn Harcsa-Pintér, Zsófia Kelemen, Zsolt |
| description | Although several synthesized icosahedral carborane fused 2D π-ring systems are known, and even considerable conjugation has been noted between them in some cases, the phenomenon itself is not fully understood. Based on the results of our computational study, it can be concluded that the 2D aromatic character of the fused (
exo
) five-membered ring is low, even in cases where significant conjugation was proposed in previous studies. Moreover, the carborane moiety constricts the bonding properties of the
exo
ring, thus prohibiting or promoting different Lewis resonance structures. These results will shed further light on the design and electronic modulation of new carborane-based materials.
We have demonstrated that carborane fused heterocycles can definitely be considered as non-2D aromatic compounds; therefore, their aromatic character was significantly overestimated in earlier studies. |
| doi_str_mv | 10.1039/d2sc03511a |
| format | Article |
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exo
) five-membered ring is low, even in cases where significant conjugation was proposed in previous studies. Moreover, the carborane moiety constricts the bonding properties of the
exo
ring, thus prohibiting or promoting different Lewis resonance structures. These results will shed further light on the design and electronic modulation of new carborane-based materials.
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exo
) five-membered ring is low, even in cases where significant conjugation was proposed in previous studies. Moreover, the carborane moiety constricts the bonding properties of the
exo
ring, thus prohibiting or promoting different Lewis resonance structures. These results will shed further light on the design and electronic modulation of new carborane-based materials.
We have demonstrated that carborane fused heterocycles can definitely be considered as non-2D aromatic compounds; therefore, their aromatic character was significantly overestimated in earlier studies.</description><subject>Aromaticity</subject><subject>Carborane</subject><subject>Chemistry</subject><subject>Conjugation</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNpdkt1LHDEUxYNUqlhf-q4E-lKEqUnuZGbShxZZ2yoIPqjPIZu5cbPMTmySabv_vbGr24-8nMD9cTiXcwl5y9kHzkCd9iJZBpJzs0P2Bat51UhQr7Z_wfbIYUpLVh4Al6J9TfagAcFk1-wTPwvjcro32YeRzjH_RBwpnFMz9lQUiWFVZtbn9UfaB0zUZxrRDMOa4i-f8md6u0BqTUIaXNE4D9GMWLkpYU8XmDEGu7YDpjdk15kh4eGzHpC7r19uZxfV1fW3y9nZVWVr0eVKsAZqDgrAqMY41bTKMOs65bioVd1ZazgXTlkhnOwEIrRSqTmzvGeWNQ4OyKeN78M0X2FvcczRDPoh-pWJax2M1_9ORr_Q9-GHVhKgFqwYvH82iOH7hCnrlU8Wh6HsFaakRQu8RGXQFvTdf-gyTHEs6xVKcN62jZSFOtlQNoaUIrptGM70U4n6XNzMfpd4VuDjv-Nv0ZfKCnC0AWKy2-mfK4BHCsOgWw</recordid><startdate>20221005</startdate><enddate>20221005</enddate><creator>Buzsáki, Dániel</creator><creator>Kovács, Máté Barnabás</creator><creator>Hümpfner, Evelyn</creator><creator>Harcsa-Pintér, Zsófia</creator><creator>Kelemen, Zsolt</creator><general>Royal Society of Chemistry</general><general>The Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0002-5631-2711</orcidid><orcidid>https://orcid.org/0000-0002-4787-9804</orcidid></search><sort><creationdate>20221005</creationdate><title>Conjugation between 3D and 2D aromaticity: does it really exist? The case of carborane-fused heterocycles</title><author>Buzsáki, Dániel ; Kovács, Máté Barnabás ; Hümpfner, Evelyn ; Harcsa-Pintér, Zsófia ; Kelemen, Zsolt</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c428t-2063413933a96af9679a0cf89f124948cca112f9c22f582ee37599b0c1d0c06f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Aromaticity</topic><topic>Carborane</topic><topic>Chemistry</topic><topic>Conjugation</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Buzsáki, Dániel</creatorcontrib><creatorcontrib>Kovács, Máté Barnabás</creatorcontrib><creatorcontrib>Hümpfner, Evelyn</creatorcontrib><creatorcontrib>Harcsa-Pintér, Zsófia</creatorcontrib><creatorcontrib>Kelemen, Zsolt</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Buzsáki, Dániel</au><au>Kovács, Máté Barnabás</au><au>Hümpfner, Evelyn</au><au>Harcsa-Pintér, Zsófia</au><au>Kelemen, Zsolt</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Conjugation between 3D and 2D aromaticity: does it really exist? The case of carborane-fused heterocycles</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2022-10-05</date><risdate>2022</risdate><volume>13</volume><issue>38</issue><spage>11388</spage><epage>11393</epage><pages>11388-11393</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>Although several synthesized icosahedral carborane fused 2D π-ring systems are known, and even considerable conjugation has been noted between them in some cases, the phenomenon itself is not fully understood. Based on the results of our computational study, it can be concluded that the 2D aromatic character of the fused (
exo
) five-membered ring is low, even in cases where significant conjugation was proposed in previous studies. Moreover, the carborane moiety constricts the bonding properties of the
exo
ring, thus prohibiting or promoting different Lewis resonance structures. These results will shed further light on the design and electronic modulation of new carborane-based materials.
We have demonstrated that carborane fused heterocycles can definitely be considered as non-2D aromatic compounds; therefore, their aromatic character was significantly overestimated in earlier studies.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>36320586</pmid><doi>10.1039/d2sc03511a</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-5631-2711</orcidid><orcidid>https://orcid.org/0000-0002-4787-9804</orcidid><oa>free_for_read</oa></addata></record> |
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| source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
| subjects | Aromaticity Carborane Chemistry Conjugation |
| title | Conjugation between 3D and 2D aromaticity: does it really exist? The case of carborane-fused heterocycles |
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