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dc.contributor.authorDas, Soumyajit
dc.contributor.authorLee, Sangsu
dc.contributor.authorSon, Minjung
dc.contributor.authorZhu, Xiaojian
dc.contributor.authorZhang, Wenhua
dc.contributor.authorZheng, Bin
dc.contributor.authorHu, Pan
dc.contributor.authorZeng, Zebing
dc.contributor.authorSun, Zhe
dc.contributor.authorZeng, Wangdong
dc.contributor.authorLi, Runwei
dc.contributor.authorHuang, Kuo-Wei
dc.contributor.authorDing, Jun
dc.contributor.authorKim, Dongho
dc.contributor.authorWu, Jishan
dc.date.accessioned2015-08-03T12:05:15Z
dc.date.available2015-08-03T12:05:15Z
dc.date.issued2014-07-23
dc.identifier.citationDas, S., Lee, S., Son, M., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). para-Quinodimethane-Bridged Perylene Dimers and Pericondensed Quaterrylenes: The Effect of the Fusion Mode on the Ground States and Physical Properties. Chemistry - A European Journal, 20(36), 11410–11420. doi:10.1002/chem.201402831
dc.identifier.issn09476539
dc.identifier.doi10.1002/chem.201402831
dc.identifier.urihttp://hdl.handle.net/10754/563659
dc.description.abstractPolycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcalmol-1), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds. A matter of fusion mode! Fusion of a para-quinodimethane (p-QDM) subunit at the peri and β positions of perylene dimers leads to systems with different ground states, that is, open and closed shell (see picture). These systems showed large two-photon absorption cross sections and ultrafast excited-state dynamics relative to their corresponding pericondensed aromatic quaterrylene counterparts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
dc.description.sponsorshipJ.W. acknowledges the financial support from the BMRC grant (10/1/21/19/642), MOE Tier 2 grant (MOE2011-T2-2-130), MINDEF-NUS JPP Grant (12-02-05), and IMRE Core funding (IMRE/13-1C0205). The work at Yonsei University was supported by a Mid-career Researcher Program (2010-0029668) and 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. H. acknowledges financial support from KAUST. We thank Koh Lip Lin, Tan Geok Kheng, and Hong Yimian for the crystallographic analysis of 4.
dc.publisherWiley
dc.subjectaromaticity
dc.subjectpolycycles
dc.subjectradicals
dc.subjectrylene
dc.subjectzethrene
dc.titlePara-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical properties
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentHomogeneous Catalysis Laboratory (HCL)
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalChemistry - A European Journal
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, 117543 Singapore, Singapore
dc.contributor.institutionDepartment of Chemistry, Yonsei University, Seoul 120-749, South Korea
dc.contributor.institutionKey Laboratory of Magnetic Materials and Devices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
dc.contributor.institutionInstitute of Materials Research and Engineering, ASTAR, 3 Research Link, 117602 Singapore, Singapore
dc.contributor.institutionDepartment of Materials Science and Engineering, National University of Singapore, 119260 Singapore, Singapore
kaust.personZheng, Bin
kaust.personHuang, Kuo-Wei
dc.relation.issupplementedbyDOI:10.5517/cc11mz9y
dc.relation.issupplementedbyDOI:10.5517/cc11mzbz
display.relations<b> Is Supplemented By:</b> <br/> <ul><li><i>[Dataset]</i> <br/> Das, S., Lee, S., Son, M., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). CCDC 972510: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11mz9y. DOI: <a href="https://doi.org/10.5517/cc11mz9y">10.5517/cc11mz9y</a> HANDLE: <a href="http://hdl.handle.net/10754/624283">10754/624283</a></li><li><i>[Dataset]</i> <br/> Das, S., Lee, S., Son, M., Zhu, X., Zhang, W., Zheng, B., … Wu, J. (2014). CCDC 972511: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11mzbz. DOI: <a href="https://doi.org/10.5517/cc11mzbz">10.5517/cc11mzbz</a> HANDLE: <a href="http://hdl.handle.net/10754/624284">10754/624284</a></li></ul>
dc.date.published-online2014-07-23
dc.date.published-print2014-09-01


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