Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

Handle URI:
http://hdl.handle.net/10754/563140
Title:
Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids
Authors:
Sun, Zhe; Lee, Sangsu; Park, Kyuhyung; Zhu, Xiaojian; Zhang, Wenhua; Zheng, Bin; Hu, Pan; Zeng, Zebing; Das, Soumyajit; Li, Yuan; Chi, Chunyan; Li, Runwei; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Ding, Jun; Kim, Dongho; Wu, Jishan
Abstract:
Clar's aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar's aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; HCL
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
4-Dec-2013
DOI:
10.1021/ja410279j
Type:
Article
ISSN:
00027863
Sponsors:
J.W. acknowledges financial support from a MOE Tier 2 grant (MOE2011-T2-2-130) and IMRE Core funding (IMRE/13-1C0205). The work at Yonsei University was supported by the Midcareer Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K.-W.H. acknowledges financial support from KAUST.
Is Supplemented By:
Sun, Z., Lee, S., Park, K. H., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). CCDC 954025: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc110r0t; DOI:10.5517/cc110r0t; HANDLE:http://hdl.handle.net/10754/624247; Sun, Z., Lee, S., Park, K. H., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). CCDC 954023: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc110qyq; DOI:10.5517/cc110qyq; HANDLE:http://hdl.handle.net/10754/624246
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorSun, Zheen
dc.contributor.authorLee, Sangsuen
dc.contributor.authorPark, Kyuhyungen
dc.contributor.authorZhu, Xiaojianen
dc.contributor.authorZhang, Wenhuaen
dc.contributor.authorZheng, Binen
dc.contributor.authorHu, Panen
dc.contributor.authorZeng, Zebingen
dc.contributor.authorDas, Soumyajiten
dc.contributor.authorLi, Yuanen
dc.contributor.authorChi, Chunyanen
dc.contributor.authorLi, Runweien
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorDing, Junen
dc.contributor.authorKim, Donghoen
dc.contributor.authorWu, Jishanen
dc.date.accessioned2015-08-03T11:36:43Zen
dc.date.available2015-08-03T11:36:43Zen
dc.date.issued2013-12-04en
dc.identifier.issn00027863en
dc.identifier.doi10.1021/ja410279jen
dc.identifier.urihttp://hdl.handle.net/10754/563140en
dc.description.abstractClar's aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar's aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.en
dc.description.sponsorshipJ.W. acknowledges financial support from a MOE Tier 2 grant (MOE2011-T2-2-130) and IMRE Core funding (IMRE/13-1C0205). The work at Yonsei University was supported by the Midcareer Researcher Program (2010-0029668) and the Global Research Laboratory (2013K1A1A2A02050183) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT (Information and Communication Technologies) and Future Planning. K.-W.H. acknowledges financial support from KAUST.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleDibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloidsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
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.institutionDepartment of Chemistry, Yonsei University, Seoul 120-749, South Koreaen
dc.contributor.institutionKey Laboratory of Magnetic Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Chinaen
dc.contributor.institutionInstitute of Materials Research and Engineering, A STAR, 3 Research Link, 117602 Singapore, Singaporeen
dc.contributor.institutionDepartment of Materials Science and Engineering, National University of Singapore, 119260 Singapore, Singaporeen
kaust.authorZheng, Binen
kaust.authorHuang, Kuo-Weien
dc.relation.isSupplementedBySun, Z., Lee, S., Park, K. H., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). CCDC 954025: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc110r0ten
dc.relation.isSupplementedByDOI:10.5517/cc110r0ten
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624247en
dc.relation.isSupplementedBySun, Z., Lee, S., Park, K. H., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). CCDC 954023: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc110qyqen
dc.relation.isSupplementedByDOI:10.5517/cc110qyqen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624246en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.