Publication

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

조회수 : 9 등록일 : 2019.04.15 00:00

저자 : Jo, H (Jo, Hongil); Ok, KM (Ok, Kang Min)
출처 : CHEMISTRY-A EUROPEAN JOURNAL
출판일 : 2019.03.07


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


Firmansyah, D (Firmansyah, Dikhi)1 ] Hong, SJ (Hong, Seong-Jin)1 ] Dutta, R (Dutta, Ranjan)1 ] He, Q (He, Qing)5 ] Bae, J (Bae, Jinhee)2 ] Jo, H(Jo, Hongil)3 ] Kim, H (Kim, Hakwon)4 ] Ok, KM (Ok, Kang Min)3 ] Lynch, VM (Lynch, Vincent M.)5 ] Byon, HR (Byon, Hye Ryung)2 ] Sessler, JL (Sessler, Jonathan L.)5 ] Lee, CH (Lee, Chang-Hee)1 ]


[ 1 ] Kangwon Natl Univ, Dept Chem, Chunchon 24341, South Korea
[ 2 ] Korea Adv Inst Sci & Technol, NanoCentury, Adv Battery Ctr, KAIST Inst,Dept Chem, 291 Daehok Ro, Daejeon 34141, South Korea
[ 3 ] Sogang Univ, Dept Chem, 35 Baekbeom Ro, Seoul 04107, South Korea
[ 4 ] Kyung Hee Univ, Dept Chem, Yongin 17104, South Korea
[ 5 ] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA



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.






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