Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons.
Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift o...
| Publicado en: | Journal of the American Chemical Society Vol. 138; no. 8; pp. 2602 - 2609 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
3/2/2016
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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=113856414&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 113856414 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: 3/2/2016 vid: 138 iid: 8 pid: 997 pub: American Chemical Society artinfo: ui: 113856414 10.1021/jacs.5b10399 ppf: 2602 ppct: 7 formats: tig: atl: Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons. aug: au: Junzhi Liu Akimitsu Narita Silvio Osella Wen Zhang Schollmeyer, Dieter Beljonne, David Feng, Xinliang Müllen, Klaus affil: Max-Planck Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany Laboratory for Chemistry of Novel Materials, University of Mons, Place du Parc 20, B-7000 Mons, Belgium Institut für Organische Chemie, Universität Mainz, Düsbergweg 10-14, 55099 Mainz, Germany Center for Advancing Electronics Dresden (CFAED) & Department of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany su: Polycyclic aromatic hydrocarbons Aryl group Single crystals Density functional theory Optoelectronic devices sug: subj: Polycyclic aromatic hydrocarbons Aryl group Single crystals Density functional theory Optoelectronic devices ab: Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be rationalized by density functional theory (DFT) calculations. The theoretical results suggest that the formation of the bistetracene analogue with five-membered rings is kinetically controlled while an "expected" product with six-membered rings is thermodynamically more favored. These experimental and theoretical results provide further insights into the still controversial mechanism of the Scholl reaction as well as open up an unprecedented entry to extend the variety of PAHs by programing otherwise unpredictable rearrangements during the Scholl reaction. 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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