Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

Handle URI:
http://hdl.handle.net/10754/593178
Title:
Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity
Authors:
Hu, Pan; Lee, Sangsu; Herng, Tun Seng; Aratani, Naoki; Goncalves, Theo; Qi, Qingbiao; Shi, Xueliang; Yamada, Hiroko; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Ding, Jun; Kim, Dongho; Wu, Jishan
Abstract:
Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Citation:
Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity 2015 Journal of the American Chemical Society
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
30-Dec-2015
DOI:
10.1021/jacs.5b12532
Type:
Article
ISSN:
0002-7863; 1520-5126
Is Supplemented By:
Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434045: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47jg; DOI:10.5517/cc1k47jg; HANDLE:http://hdl.handle.net/10754/624480; Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434046: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47kh; DOI:10.5517/cc1k47kh; HANDLE:http://hdl.handle.net/10754/624481; Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434048: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47mk; DOI:10.5517/cc1k47mk; HANDLE:http://hdl.handle.net/10754/624483; Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1436511: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k6t2n; DOI:10.5517/cc1k6t2n; HANDLE:http://hdl.handle.net/10754/624484; Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1436512: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k6t3p; DOI:10.5517/cc1k6t3p; HANDLE:http://hdl.handle.net/10754/624485; Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1436513: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k6t4q; DOI:10.5517/cc1k6t4q; HANDLE:http://hdl.handle.net/10754/624486; Hu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434047: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47lj; DOI:10.5517/cc1k47lj; HANDLE:http://hdl.handle.net/10754/624482
Additional Links:
http://pubs.acs.org/doi/10.1021/jacs.5b12532
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorHu, Panen
dc.contributor.authorLee, Sangsuen
dc.contributor.authorHerng, Tun Sengen
dc.contributor.authorAratani, Naokien
dc.contributor.authorGoncalves, Theoen
dc.contributor.authorQi, Qingbiaoen
dc.contributor.authorShi, Xueliangen
dc.contributor.authorYamada, Hirokoen
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorDing, Junen
dc.contributor.authorKim, Donghoen
dc.contributor.authorWu, Jishanen
dc.date.accessioned2016-01-10T10:19:17Zen
dc.date.available2016-01-10T10:19:17Zen
dc.date.issued2015-12-30en
dc.identifier.citationTowards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity 2015 Journal of the American Chemical Societyen
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.5b12532en
dc.identifier.urihttp://hdl.handle.net/10754/593178en
dc.description.abstractOpen-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/jacs.5b12532en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/jacs.5b12532.en
dc.titleTowards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivityen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singaporeen
dc.contributor.institutionSpectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120- 749, Koreaen
dc.contributor.institutionDepartment of Materials Science & Engineering, National University of Singapore, 119260, Singaporeen
dc.contributor.institutionGraduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama-cho, Ikoma 630-0192, Japanen
dc.contributor.institutionInstitute of Materials Research and Engineering, A*STAR, 2 Fusionopolis Way, Innovis, #08-03, 117602, Singaporeen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorGoncalves, Theoen
kaust.authorHuang, Kuo-Weien
dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434045: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47jgen
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dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624480en
dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434046: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47khen
dc.relation.isSupplementedByDOI:10.5517/cc1k47khen
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dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434048: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47mken
dc.relation.isSupplementedByDOI:10.5517/cc1k47mken
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624483en
dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1436511: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k6t2nen
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dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624484en
dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1436512: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k6t3pen
dc.relation.isSupplementedByDOI:10.5517/cc1k6t3pen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624485en
dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1436513: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k6t4qen
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dc.relation.isSupplementedByHu, P., Lee, S., Seng, H. T., Aratani, N., Zheng, B., Yamada, H., … Wu, J. (2016). CCDC 1434047: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1k47ljen
dc.relation.isSupplementedByDOI:10.5517/cc1k47ljen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624482en
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