Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical properties

Handle URI:
http://hdl.handle.net/10754/563659
Title:
Para-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical properties
Authors:
Das, Soumyajit; Lee, Sangsu; Son, Minjung; Zhu, Xiaojian; Zhang, Wenhua; Zheng, Bin; Hu, Pan; Zeng, Zebing; Sun, Zhe; Zeng, Wangdong; Li, Runwei; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Ding, Jun; Kim, Dongho; Wu, Jishan
Abstract:
Polycyclic 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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; HCL
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
23-Jul-2014
DOI:
10.1002/chem.201402831
Type:
Article
ISSN:
09476539
Sponsors:
J.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.
Is Supplemented By:
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:10.5517/cc11mz9y; HANDLE:http://hdl.handle.net/10754/624283; 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:10.5517/cc11mzbz; HANDLE:http://hdl.handle.net/10754/624284
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.authorDas, Soumyajiten
dc.contributor.authorLee, Sangsuen
dc.contributor.authorSon, Minjungen
dc.contributor.authorZhu, Xiaojianen
dc.contributor.authorZhang, Wenhuaen
dc.contributor.authorZheng, Binen
dc.contributor.authorHu, Panen
dc.contributor.authorZeng, Zebingen
dc.contributor.authorSun, Zheen
dc.contributor.authorZeng, Wangdongen
dc.contributor.authorLi, Runweien
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorDing, Junen
dc.contributor.authorKim, Donghoen
dc.contributor.authorWu, Jishanen
dc.date.accessioned2015-08-03T12:05:15Zen
dc.date.available2015-08-03T12:05:15Zen
dc.date.issued2014-07-23en
dc.identifier.issn09476539en
dc.identifier.doi10.1002/chem.201402831en
dc.identifier.urihttp://hdl.handle.net/10754/563659en
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.en
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.en
dc.publisherWiley-Blackwellen
dc.subjectaromaticityen
dc.subjectpolycyclesen
dc.subjectradicalsen
dc.subjectryleneen
dc.subjectzethreneen
dc.titlePara-quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: The effect of the fusion mode on the ground states and physical propertiesen
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.journalChemistry - A European Journalen
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, ASTAR, 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.isSupplementedByDas, 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/cc11mz9yen
dc.relation.isSupplementedByDOI:10.5517/cc11mz9yen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624283en
dc.relation.isSupplementedByDas, 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/cc11mzbzen
dc.relation.isSupplementedByDOI:10.5517/cc11mzbzen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624284en
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