Competing Annulene and Radialene Structures in a Single Anti-Aromatic Molecule Studied by High-Resolution Atomic Force Microscopy

According to Hückel theory, an anti-aromatic molecule possessing (4n)π-electrons becomes unstable. Although the stabilization has been demonstrated by radialene-type structuresfusing aromatic rings to anti-aromatic ringsin solution, such molecules have never been studied at a single molecular le...

Ausführliche Beschreibung

Gespeichert in:

Bibliographische Detailangaben
Veröffentlicht in:	ACS nano 2017-08, Vol.11 (8), p.8122-8130
Hauptverfasser:	Kawai, Shigeki, Takahashi, Keisuke, Ito, Shingo, Pawlak, Rémy, Meier, Tobias, Spijker, Peter, Canova, Filippo Federici, Tracey, John, Nozaki, Kyoko, Foster, Adam S, Meyer, Ernst
Format:	Artikel
Sprache:	eng
Online-Zugang:	Volltext
Tags:	Tag hinzufügen Keine Tags, Fügen Sie den ersten Tag hinzu!

container_end_page	8130
container_issue	8
container_start_page	8122
container_title	ACS nano
container_volume	11
creator	Kawai, Shigeki Takahashi, Keisuke Ito, Shingo Pawlak, Rémy Meier, Tobias Spijker, Peter Canova, Filippo Federici Tracey, John Nozaki, Kyoko Foster, Adam S Meyer, Ernst
description	According to Hückel theory, an anti-aromatic molecule possessing (4n)π-electrons becomes unstable. Although the stabilization has been demonstrated by radialene-type structuresfusing aromatic rings to anti-aromatic ringsin solution, such molecules have never been studied at a single molecular level. Here, we synthesize a cyclobutadiene derivative, dibenzo[b,h]biphenylene, by an on-surface intramolecular reaction. With a combination of high-resolution atomic force microscopy and density functional theory calculations, we found that a radialene structure significantly reduces the anti-aromaticity of the cyclobutadiene core, extracting π-electrons, while the small four-membered cyclic structure keeps a high density of the total charge.
doi_str_mv	10.1021/acsnano.7b02973
format	Article
fullrecord	<record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1920203081</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1920203081</sourcerecordid><originalsourceid>FETCH-LOGICAL-a399t-14abdfcd90ea67cd07592a1ae8eff94a84848d3393fd6d5d49ed8de01b09717e3</originalsourceid><addsrcrecordid>eNp1kMtLAzEQxoMoWqtnb5KjINsmu-1mcyzFF1gEH-BtySazGtlN1jwOPfqfm9rqTeYwM_D7PmY-hM4omVCS06mQ3ghjJ6whOWfFHhpRXpQZqcrX_b95To_QsfcfhMxZxcpDdJRXjOY5L0foa2n7AYI2b3hhTOzAABZG4UehtPjZnoKLMkQHHmuDBX5KbAeJDjpbONuLoCVe2Q5kUic6Kg0KN2t8q9_es0fwtotBW4MXwfYJvbZOAl5p6ayXdlifoINWdB5Od32MXq6vnpe32f3Dzd1ycZ-JgvOQ0ZloVCsVJyBKJhVhc54LKqCCtuUzUc1SqaLgRatKNVczDqpSQGhDOKMMijG62PoOzn5G8KHutZfQdcKAjb6mPCc5KUhFEzrdopsbvYO2HpzuhVvXlNSb3Otd7vUu96Q435nHpgf1x_8GnYDLLZCU9YeNzqRf_7X7Bt42kNA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1920203081</pqid></control><display><type>article</type><title>Competing Annulene and Radialene Structures in a Single Anti-Aromatic Molecule Studied by High-Resolution Atomic Force Microscopy</title><source>ACS Publications</source><creator>Kawai, Shigeki ; Takahashi, Keisuke ; Ito, Shingo ; Pawlak, Rémy ; Meier, Tobias ; Spijker, Peter ; Canova, Filippo Federici ; Tracey, John ; Nozaki, Kyoko ; Foster, Adam S ; Meyer, Ernst</creator><creatorcontrib>Kawai, Shigeki ; Takahashi, Keisuke ; Ito, Shingo ; Pawlak, Rémy ; Meier, Tobias ; Spijker, Peter ; Canova, Filippo Federici ; Tracey, John ; Nozaki, Kyoko ; Foster, Adam S ; Meyer, Ernst</creatorcontrib><description>According to Hückel theory, an anti-aromatic molecule possessing (4n)π-electrons becomes unstable. Although the stabilization has been demonstrated by radialene-type structuresfusing aromatic rings to anti-aromatic ringsin solution, such molecules have never been studied at a single molecular level. Here, we synthesize a cyclobutadiene derivative, dibenzo[b,h]biphenylene, by an on-surface intramolecular reaction. With a combination of high-resolution atomic force microscopy and density functional theory calculations, we found that a radialene structure significantly reduces the anti-aromaticity of the cyclobutadiene core, extracting π-electrons, while the small four-membered cyclic structure keeps a high density of the total charge.</description><identifier>ISSN: 1936-0851</identifier><identifier>EISSN: 1936-086X</identifier><identifier>DOI: 10.1021/acsnano.7b02973</identifier><identifier>PMID: 28712296</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>ACS nano, 2017-08, Vol.11 (8), p.8122-8130</ispartof><rights>Copyright © 2017 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a399t-14abdfcd90ea67cd07592a1ae8eff94a84848d3393fd6d5d49ed8de01b09717e3</citedby><cites>FETCH-LOGICAL-a399t-14abdfcd90ea67cd07592a1ae8eff94a84848d3393fd6d5d49ed8de01b09717e3</cites><orcidid>0000-0003-1776-4608 ; 0000-0001-8295-7241 ; 0000-0001-5371-5905 ; 0000-0003-0606-5131 ; 0000-0002-0321-5299 ; 0000-0003-2128-0120</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acsnano.7b02973$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acsnano.7b02973$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/28712296$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Kawai, Shigeki</creatorcontrib><creatorcontrib>Takahashi, Keisuke</creatorcontrib><creatorcontrib>Ito, Shingo</creatorcontrib><creatorcontrib>Pawlak, Rémy</creatorcontrib><creatorcontrib>Meier, Tobias</creatorcontrib><creatorcontrib>Spijker, Peter</creatorcontrib><creatorcontrib>Canova, Filippo Federici</creatorcontrib><creatorcontrib>Tracey, John</creatorcontrib><creatorcontrib>Nozaki, Kyoko</creatorcontrib><creatorcontrib>Foster, Adam S</creatorcontrib><creatorcontrib>Meyer, Ernst</creatorcontrib><title>Competing Annulene and Radialene Structures in a Single Anti-Aromatic Molecule Studied by High-Resolution Atomic Force Microscopy</title><title>ACS nano</title><addtitle>ACS Nano</addtitle><description>According to Hückel theory, an anti-aromatic molecule possessing (4n)π-electrons becomes unstable. Although the stabilization has been demonstrated by radialene-type structuresfusing aromatic rings to anti-aromatic ringsin solution, such molecules have never been studied at a single molecular level. Here, we synthesize a cyclobutadiene derivative, dibenzo[b,h]biphenylene, by an on-surface intramolecular reaction. With a combination of high-resolution atomic force microscopy and density functional theory calculations, we found that a radialene structure significantly reduces the anti-aromaticity of the cyclobutadiene core, extracting π-electrons, while the small four-membered cyclic structure keeps a high density of the total charge.</description><issn>1936-0851</issn><issn>1936-086X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNp1kMtLAzEQxoMoWqtnb5KjINsmu-1mcyzFF1gEH-BtySazGtlN1jwOPfqfm9rqTeYwM_D7PmY-hM4omVCS06mQ3ghjJ6whOWfFHhpRXpQZqcrX_b95To_QsfcfhMxZxcpDdJRXjOY5L0foa2n7AYI2b3hhTOzAABZG4UehtPjZnoKLMkQHHmuDBX5KbAeJDjpbONuLoCVe2Q5kUic6Kg0KN2t8q9_es0fwtotBW4MXwfYJvbZOAl5p6ayXdlifoINWdB5Od32MXq6vnpe32f3Dzd1ycZ-JgvOQ0ZloVCsVJyBKJhVhc54LKqCCtuUzUc1SqaLgRatKNVczDqpSQGhDOKMMijG62PoOzn5G8KHutZfQdcKAjb6mPCc5KUhFEzrdopsbvYO2HpzuhVvXlNSb3Otd7vUu96Q435nHpgf1x_8GnYDLLZCU9YeNzqRf_7X7Bt42kNA</recordid><startdate>20170822</startdate><enddate>20170822</enddate><creator>Kawai, Shigeki</creator><creator>Takahashi, Keisuke</creator><creator>Ito, Shingo</creator><creator>Pawlak, Rémy</creator><creator>Meier, Tobias</creator><creator>Spijker, Peter</creator><creator>Canova, Filippo Federici</creator><creator>Tracey, John</creator><creator>Nozaki, Kyoko</creator><creator>Foster, Adam S</creator><creator>Meyer, Ernst</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-1776-4608</orcidid><orcidid>https://orcid.org/0000-0001-8295-7241</orcidid><orcidid>https://orcid.org/0000-0001-5371-5905</orcidid><orcidid>https://orcid.org/0000-0003-0606-5131</orcidid><orcidid>https://orcid.org/0000-0002-0321-5299</orcidid><orcidid>https://orcid.org/0000-0003-2128-0120</orcidid></search><sort><creationdate>20170822</creationdate><title>Competing Annulene and Radialene Structures in a Single Anti-Aromatic Molecule Studied by High-Resolution Atomic Force Microscopy</title><author>Kawai, Shigeki ; Takahashi, Keisuke ; Ito, Shingo ; Pawlak, Rémy ; Meier, Tobias ; Spijker, Peter ; Canova, Filippo Federici ; Tracey, John ; Nozaki, Kyoko ; Foster, Adam S ; Meyer, Ernst</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a399t-14abdfcd90ea67cd07592a1ae8eff94a84848d3393fd6d5d49ed8de01b09717e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kawai, Shigeki</creatorcontrib><creatorcontrib>Takahashi, Keisuke</creatorcontrib><creatorcontrib>Ito, Shingo</creatorcontrib><creatorcontrib>Pawlak, Rémy</creatorcontrib><creatorcontrib>Meier, Tobias</creatorcontrib><creatorcontrib>Spijker, Peter</creatorcontrib><creatorcontrib>Canova, Filippo Federici</creatorcontrib><creatorcontrib>Tracey, John</creatorcontrib><creatorcontrib>Nozaki, Kyoko</creatorcontrib><creatorcontrib>Foster, Adam S</creatorcontrib><creatorcontrib>Meyer, Ernst</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>ACS nano</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kawai, Shigeki</au><au>Takahashi, Keisuke</au><au>Ito, Shingo</au><au>Pawlak, Rémy</au><au>Meier, Tobias</au><au>Spijker, Peter</au><au>Canova, Filippo Federici</au><au>Tracey, John</au><au>Nozaki, Kyoko</au><au>Foster, Adam S</au><au>Meyer, Ernst</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Competing Annulene and Radialene Structures in a Single Anti-Aromatic Molecule Studied by High-Resolution Atomic Force Microscopy</atitle><jtitle>ACS nano</jtitle><addtitle>ACS Nano</addtitle><date>2017-08-22</date><risdate>2017</risdate><volume>11</volume><issue>8</issue><spage>8122</spage><epage>8130</epage><pages>8122-8130</pages><issn>1936-0851</issn><eissn>1936-086X</eissn><abstract>According to Hückel theory, an anti-aromatic molecule possessing (4n)π-electrons becomes unstable. Although the stabilization has been demonstrated by radialene-type structuresfusing aromatic rings to anti-aromatic ringsin solution, such molecules have never been studied at a single molecular level. Here, we synthesize a cyclobutadiene derivative, dibenzo[b,h]biphenylene, by an on-surface intramolecular reaction. With a combination of high-resolution atomic force microscopy and density functional theory calculations, we found that a radialene structure significantly reduces the anti-aromaticity of the cyclobutadiene core, extracting π-electrons, while the small four-membered cyclic structure keeps a high density of the total charge.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>28712296</pmid><doi>10.1021/acsnano.7b02973</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0003-1776-4608</orcidid><orcidid>https://orcid.org/0000-0001-8295-7241</orcidid><orcidid>https://orcid.org/0000-0001-5371-5905</orcidid><orcidid>https://orcid.org/0000-0003-0606-5131</orcidid><orcidid>https://orcid.org/0000-0002-0321-5299</orcidid><orcidid>https://orcid.org/0000-0003-2128-0120</orcidid></addata></record>
fulltext	fulltext
identifier	ISSN: 1936-0851
ispartof	ACS nano, 2017-08, Vol.11 (8), p.8122-8130
issn	1936-0851 1936-086X
language	eng
recordid	cdi_proquest_miscellaneous_1920203081
source	ACS Publications
title	Competing Annulene and Radialene Structures in a Single Anti-Aromatic Molecule Studied by High-Resolution Atomic Force Microscopy
url	https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-04T17%3A35%3A01IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Competing%20Annulene%20and%20Radialene%20Structures%20in%20a%20Single%20Anti-Aromatic%20Molecule%20Studied%20by%20High-Resolution%20Atomic%20Force%20Microscopy&rft.jtitle=ACS%20nano&rft.au=Kawai,%20Shigeki&rft.date=2017-08-22&rft.volume=11&rft.issue=8&rft.spage=8122&rft.epage=8130&rft.pages=8122-8130&rft.issn=1936-0851&rft.eissn=1936-086X&rft_id=info:doi/10.1021/acsnano.7b02973&rft_dat=%3Cproquest_cross%3E1920203081%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1920203081&rft_id=info:pmid/28712296&rfr_iscdi=true