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dc.contributor.authorHu, Pan
dc.contributor.authorLee, Sangsu
dc.contributor.authorPark, Kyu Hyung
dc.contributor.authorDas, Soumyajit
dc.contributor.authorHerng, Tun Seng
dc.contributor.authorGoncalves, Theo
dc.contributor.authorHuang, Kuo-Wei
dc.contributor.authorDing, Jun
dc.contributor.authorKim, Dongho
dc.contributor.authorWu, Jishan
dc.date.accessioned2016-03-15T13:53:09Z
dc.date.available2016-03-15T13:53:09Z
dc.date.issued2016-03-21
dc.identifier.citationOctazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure 2016 The Journal of Organic Chemistry
dc.identifier.issn0022-3263
dc.identifier.issn1520-6904
dc.identifier.pmid26966788
dc.identifier.doi10.1021/acs.joc.6b00172
dc.identifier.urihttp://hdl.handle.net/10754/601361
dc.description.abstractThe fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.
dc.description.sponsorshipJ. W. acknowledges the financial support from the MOE Tier 3 Programme (MOE2014-T3-1-004), Tier 2 grant (MOE2014-T2-1- 080) and A*STAR JCO grant (1431AFG100). This work at Yonsei University was supported by the Global Frontier R&D Program on Center for Multiscale Energy System funded by the National Research Foundation under the Ministry of Science, ICT & Future, Korea (NRF-2014M3A6A7060583). We thank Dr. Tan Geok Kheng and Dr. Bruno Donnadieu for the crystallographic analysis.
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.joc.6b00172
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, 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/abs/10.1021/acs.joc.6b00172.
dc.titleOctazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure
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.journalThe Journal of Organic Chemistry
dc.eprint.versionPost-print
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore
dc.contributor.institutionSpectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei Univer sity, Seoul 120# 749, Korea
dc.contributor.institutionDepartment of Materials Science & Engineering, National University of Singapore, 119260, Singapore
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)
kaust.personGoncalves, Theo
kaust.personHuang, Kuo-Wei
dc.relation.issupplementedbyDOI:10.5517/ccdc.csd.cc1jm5kw
refterms.dateFOA2017-03-11T00:00:00Z
display.relations<b> Is Supplemented By:</b> <br/> <ul><li><i>[Dataset]</i> <br/> Hu, P., Lee, S., Park, K. H., Das, S., Herng, T. S., Gonçalves, T. P., … Wu, J. (2016). CCDC 1418608: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1jm5kw. DOI: <a href="https://doi.org/10.5517/ccdc.csd.cc1jm5kw">10.5517/ccdc.csd.cc1jm5kw</a> HANDLE: <a href="http://hdl.handle.net/10754/624512">10754/624512</a></li></ul>
dc.date.published-online2016-03-21
dc.date.published-print2016-04


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