Stable tetrabenzo-Chichibabin's hydrocarbons: Tunable ground state and unusual transition between their closed-shell and open-shell resonance forms

Handle URI:
http://hdl.handle.net/10754/562319
Title:
Stable tetrabenzo-Chichibabin's hydrocarbons: Tunable ground state and unusual transition between their closed-shell and open-shell resonance forms
Authors:
Zeng, Zebing; Sung, Youngmo; Bao, Nina; Tan, Davin; Lee, Richmond; Zafra, José Luis; Lee, Byungsun; Ishida, Masatoshi; Ding, Jun; Lõpez Navarrete, Juan Teodomiro; Li, Yuan; Zeng, Wangdong; Kim, Dongho; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Webster, Richard D.; Casado, Juan; Wu, Jishan
Abstract:
Stable open-shell polycyclic aromatic hydrocarbons (PAHs) are of fundamental interest due to their unique electronic, optical, and magnetic properties and promising applications in materials sciences. Chichibabin's hydrocarbon as a classical open-shell PAH has been investigated for a long time. However, most of the studies are complicated by their inherent high reactivity. In this work, two new stable benzannulated Chichibabin's hydrocarbons 1-CS and 2-OS were prepared, and their electronic structure and geometry in the ground state were studied by various experiments (steady-state and transient absorption spectra, NMR, electron spin resonance (ESR), superconducting quantum interference device (SQUID), FT Raman, X-ray crystallographic etc.) and density function theory (DFT) calculations. 1-CS and 2-OS exhibited tunable ground states, with a closed-shell quinoidal structure for 1-CS and an open-shell biradical form for 2-OS. Their corresponding excited-state forms 1-OS and 2-CS were also chemically approached and showed different decay processes. The biradical 1-OS displayed an unusually slow decay to the ground state (1-CS) due to a large energy barrier (95 ± 2.5 kJ/mol) arising from severe steric hindrance during the transition from an orthogonal biradical form to a butterfly-like quinoidal form. The quick transition from the quinoidal 2-CS (excited state) to the orthogonal biradicaloid 2-OS (ground state) happened during the attempted synthesis of 2-CS. Compounds 1-CS and 2-OS can be oxidized into stable dications by FeCl 3 and/or concentrated H 2SO 4. The open-shell 2-OS also exhibited a large two-photon absorption (TPA) cross section (760 GM at 1200 nm). © 2012 American Chemical Society.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; KAUST Catalysis Center (KCC); Chemical Science Program; Physical Sciences and Engineering (PSE) Division; HCL
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
5-Sep-2012
DOI:
10.1021/ja3050579
Type:
Article
ISSN:
00027863
Sponsors:
J.W. acknowledges financial support from the BMRC-NMRC grant (no. 10/1/21/19/642), MOE Tier 2 grant (MOE2011-T2-2-130), and IMRE Core funding (IMRE/10-1P0509). The work at Yonsei University was supported by WCU (World Class University) programs (R32-2010-10217-0) and an AFSOR/APARD grant (no. FA2386-09-1-4092). K.-W.H. acknowledges financial support from KAUST. The work at the University of Malaga was supported by the Ministerio de Educacion y Ciencia (MEC) of Spain and by FEDER funds (project CTQ2009-10098 and to the Junta de Andalucia for the research project PO9-4708). We thank Dr. Tan Geok-Kheng for crystallographic analysis.
Is Supplemented By:
Zeng, Z., Sung, Y. M., Bao, N., Tan, D., Lee, R., Zafra, J. L., … Wu, J. (2013). CCDC 945080: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10qfgm; DOI:10.5517/cc10qfgm; HANDLE:http://hdl.handle.net/10754/624233; Zeng, Z., Sung, Y. M., Bao, N., Tan, D., Lee, R., Zafra, J. L., … Wu, J. (2013). CCDC 945081: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10qfhn; DOI:10.5517/cc10qfhn; HANDLE:http://hdl.handle.net/10754/624234
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorZeng, Zebingen
dc.contributor.authorSung, Youngmoen
dc.contributor.authorBao, Ninaen
dc.contributor.authorTan, Davinen
dc.contributor.authorLee, Richmonden
dc.contributor.authorZafra, José Luisen
dc.contributor.authorLee, Byungsunen
dc.contributor.authorIshida, Masatoshien
dc.contributor.authorDing, Junen
dc.contributor.authorLõpez Navarrete, Juan Teodomiroen
dc.contributor.authorLi, Yuanen
dc.contributor.authorZeng, Wangdongen
dc.contributor.authorKim, Donghoen
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorWebster, Richard D.en
dc.contributor.authorCasado, Juanen
dc.contributor.authorWu, Jishanen
dc.date.accessioned2015-08-03T10:00:42Zen
dc.date.available2015-08-03T10:00:42Zen
dc.date.issued2012-09-05en
dc.identifier.issn00027863en
dc.identifier.doi10.1021/ja3050579en
dc.identifier.urihttp://hdl.handle.net/10754/562319en
dc.description.abstractStable open-shell polycyclic aromatic hydrocarbons (PAHs) are of fundamental interest due to their unique electronic, optical, and magnetic properties and promising applications in materials sciences. Chichibabin's hydrocarbon as a classical open-shell PAH has been investigated for a long time. However, most of the studies are complicated by their inherent high reactivity. In this work, two new stable benzannulated Chichibabin's hydrocarbons 1-CS and 2-OS were prepared, and their electronic structure and geometry in the ground state were studied by various experiments (steady-state and transient absorption spectra, NMR, electron spin resonance (ESR), superconducting quantum interference device (SQUID), FT Raman, X-ray crystallographic etc.) and density function theory (DFT) calculations. 1-CS and 2-OS exhibited tunable ground states, with a closed-shell quinoidal structure for 1-CS and an open-shell biradical form for 2-OS. Their corresponding excited-state forms 1-OS and 2-CS were also chemically approached and showed different decay processes. The biradical 1-OS displayed an unusually slow decay to the ground state (1-CS) due to a large energy barrier (95 ± 2.5 kJ/mol) arising from severe steric hindrance during the transition from an orthogonal biradical form to a butterfly-like quinoidal form. The quick transition from the quinoidal 2-CS (excited state) to the orthogonal biradicaloid 2-OS (ground state) happened during the attempted synthesis of 2-CS. Compounds 1-CS and 2-OS can be oxidized into stable dications by FeCl 3 and/or concentrated H 2SO 4. The open-shell 2-OS also exhibited a large two-photon absorption (TPA) cross section (760 GM at 1200 nm). © 2012 American Chemical Society.en
dc.description.sponsorshipJ.W. acknowledges financial support from the BMRC-NMRC grant (no. 10/1/21/19/642), MOE Tier 2 grant (MOE2011-T2-2-130), and IMRE Core funding (IMRE/10-1P0509). The work at Yonsei University was supported by WCU (World Class University) programs (R32-2010-10217-0) and an AFSOR/APARD grant (no. FA2386-09-1-4092). K.-W.H. acknowledges financial support from KAUST. The work at the University of Malaga was supported by the Ministerio de Educacion y Ciencia (MEC) of Spain and by FEDER funds (project CTQ2009-10098 and to the Junta de Andalucia for the research project PO9-4708). We thank Dr. Tan Geok-Kheng for crystallographic analysis.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleStable tetrabenzo-Chichibabin's hydrocarbons: Tunable ground state and unusual transition between their closed-shell and open-shell resonance formsen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentHCLen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore, Singaporeen
dc.contributor.institutionSpectroscopy Laboratory for Functional pi-Electronic Systems, Department of Chemistry, Yonsei University, Seoul 120-749, South Koreaen
dc.contributor.institutionDepartment of Materials Science and Engineering, National University of Singapore, 119260, Singapore, Singaporeen
dc.contributor.institutionDepartment of Physical Chemistry, University of Malaga, Campus de Teatinos s/n, 229071 Malaga, Spainen
dc.contributor.institutionDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore, Singaporeen
dc.contributor.institutionInstitute of Materials Research and Engineering, A Star, 3 Research Link, 117602, Singapore, Singaporeen
kaust.authorTan, Davinen
kaust.authorLee, Richmonden
kaust.authorHuang, Kuo-Weien
dc.relation.isSupplementedByZeng, Z., Sung, Y. M., Bao, N., Tan, D., Lee, R., Zafra, J. L., … Wu, J. (2013). CCDC 945080: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10qfgmen
dc.relation.isSupplementedByDOI:10.5517/cc10qfgmen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624233en
dc.relation.isSupplementedByZeng, Z., Sung, Y. M., Bao, N., Tan, D., Lee, R., Zafra, J. L., … Wu, J. (2013). CCDC 945081: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc10qfhnen
dc.relation.isSupplementedByDOI:10.5517/cc10qfhnen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624234en
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