• Login
    View Item 
    •   Home
    • Research
    • Articles
    • View Item
    •   Home
    • Research
    • Articles
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Browse

    All of KAUSTCommunitiesIssue DateSubmit DateThis CollectionIssue DateSubmit Date

    My Account

    Login

    Quick Links

    Open Access PolicyORCID LibguideTheses and Dissertations LibguideSubmit an Item

    Statistics

    Display statistics

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

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Type
    Article
    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 cc
    Webster, Richard D.
    Casado, Juan
    Wu, Jishan
    KAUST Department
    Biological and Environmental Sciences and Engineering (BESE) Division
    Chemical Science Program
    Homogeneous Catalysis Laboratory (HCL)
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2012-08-22
    Online Publication Date
    2012-08-22
    Print Publication Date
    2012-09-05
    Permanent link to this record
    http://hdl.handle.net/10754/562319
    
    Metadata
    Show full item record
    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.
    Citation
    Zeng, Z., Sung, Y. M., Bao, N., Tan, D., Lee, R., Zafra, J. L., … Wu, J. (2012). Stable Tetrabenzo-Chichibabin’s Hydrocarbons: Tunable Ground State and Unusual Transition between Their Closed-Shell and Open-Shell Resonance Forms. Journal of the American Chemical Society, 134(35), 14513–14525. doi:10.1021/ja3050579
    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.
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/ja3050579
    Relations
    Is Supplemented By:
    • [Dataset]
      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: 10754/624233
    • [Dataset]
      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: 10754/624234
    ae974a485f413a2113503eed53cd6c53
    10.1021/ja3050579
    Scopus Count
    Collections
    Articles; Biological and Environmental Science and Engineering (BESE) Division; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

    entitlement

     
    DSpace software copyright © 2002-2022  DuraSpace
    Quick Guide | Contact Us | KAUST University Library
    Open Repository is a service hosted by 
    Atmire NV
     

    Export search results

    The export option will allow you to export the current search results of the entered query to a file. Different formats are available for download. To export the items, click on the button corresponding with the preferred download format.

    By default, clicking on the export buttons will result in a download of the allowed maximum amount of items. For anonymous users the allowed maximum amount is 50 search results.

    To select a subset of the search results, click "Selective Export" button and make a selection of the items you want to export. The amount of items that can be exported at once is similarly restricted as the full export.

    After making a selection, click one of the export format buttons. The amount of items that will be exported is indicated in the bubble next to export format.