Trapping of Stable [4n+1] pi-Electron Species from Peripherally Substituted, Conformationally Rigid, Antiaromatic Hexaphyrins

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Peripherally substituted antiaromatic naphthorosarins have been synthesized for the first time. The synthesis was accomplished by acid-catalyzed condensation of naphthobipyrrole building blocks with aromatic aldehydes. The naphthobipyrrole building blocks were synthesized by simple oxidative coupling of the corresponding pyrrole substituted aromatics. Solid-state structural analyses of the synthesized naphthorosarins revealed that the presence of meso-2,6-dichlorophenyl- and 5,6-difluoro-substitution substantially alter the geometry and properties of the naphthorosarins. The substituents affect the redox potentials as well and, in turn, the proton-coupled electron-transfer processes leading to the formation of one- and two-electron reduced forms of the corresponding naphthorosarins. One particular naphthorosarin that bears both peripheral fluorine and meso-2,6-dichlorophenyl substituents forms a stable 25 pi-electron species upon treating with TFA that was characterized by single-crystal X-ray diffraction analysis. The current study underscores how structural modifications can be used to fine-tune the electronic features of naphthorosarins, including stabilization of odd electron species.
Publisher
WILEY-V C H VERLAG GMBH
Issue Date
2019-03
Language
English
Article Type
Article
Citation

CHEMISTRY-A EUROPEAN JOURNAL, v.25, no.14, pp.3525 - 3531

ISSN
0947-6539
DOI
10.1002/chem.201900022
URI
http://hdl.handle.net/10203/254008
Appears in Collection
CH-Journal Papers(저널논문)
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