Stable 3,6-Linked Fluorenyl Radical Oligomers with Intramolecular Antiferromagnetic Coupling and Polyradical Characters.
Organic radicals display unique physical structures and could become next generation functional materials. However, design and synthesis of stable neutral radicals with a significant polyradical character has been an enormous challenge for chemists. In this work, we synthesized a series of stable 3,...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 39; pp. 13048 - 13059 |
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| Autores principales: | , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
10/5/2016
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=119225989&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 119225989 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/5/2016 vid: 138 iid: 39 pid: 997 pub: American Chemical Society artinfo: ui: 119225989 10.1021/jacs.6b08138 ppf: 13048 ppct: 11 formats: tig: atl: Stable 3,6-Linked Fluorenyl Radical Oligomers with Intramolecular Antiferromagnetic Coupling and Polyradical Characters. aug: au: Xuefeng Lu Sangsu Lee Jun Oh Kim Gopalakrishna, Tullimilli Y. Hoa Phan Tun Seng Herng Zhenglong Lim Zebing Zeng Jun Ding Dongho Kim Jishan Wu affil: Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749, Korea Department of Materials Science & Engineering, National University of Singapore, 119260, Singapore College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, People's Republic of China su: Radicals Chemists Density functional theory Molecular theory Electrochemical analysis sug: subj: Radicals Chemists Density functional theory Molecular theory Electrochemical analysis ab: Organic radicals display unique physical structures and could become next generation functional materials. However, design and synthesis of stable neutral radicals with a significant polyradical character has been an enormous challenge for chemists. In this work, we synthesized a series of stable 3,6-linked, kinetically blocked fluorenyl radical oligomers up to hexamer (FR-n, n = 1-6). Their ground-state geometric and electronic structures were systematically studied by various experimental methods including X-ray crystallographic analysis, variable temperature nuclear magnetic resonance, electron spin resonance, and superconducting quantum interference device measurements, supported by density functional theory and ab initio calculations. Moderate antiferromagnetic coupling between the fluorenyl radicals was observed, and moderate to large diradical and polyradical characters were calculated from dimer onward. Furthermore, their photophysical properties were estimated by steady-state, transient absorption, and two-photon absorption measurements, and their electrochemical properties were investigated by cyclic voltammetry/differential pulse voltammetry and spectro-electrochemical measurements. A clear chain length dependence of their optical, electrochemical, and magnetic properties was found for the oligomers with an odd or even number of spin centers, respectively. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2016 holdings: @attributes: islocal: N |
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