title: Porphyrin Analogues of a Trityl Cation and Anion.
abstract: Porphyrin-stabilized meso- or β-carbocations were generated upon treatment of the corresponding bis(4-tert-butylphenyl)porphyrinylcarbinols with trifluoroacetic acid (TFA). Bis(4-tert-butylphenyl)porphyrinylcarbinols were treated with TFA to generate the corresponding carbocations stabilized by a meso- or β-porphyrinyl group. The meso-porphyrinylmethyl carbocation displayed more effective charge delocalization with decreasing aromaticity compared with the β-porphyrinylmethyl carbocation. A propeller-like porphyrin trimer, tris(β-porphyrinyl)carbinol, was also synthesized and converted to the corresponding cation that displayed a more intensified absorption reaching over the NIR region. meso-Porphyrinylmethyl carbanion was generated as a stable species upon deprotonation of bis(4-tert-butylphenyl)(meso-porphyrinyl)methane with potassium bis(trimethylsilyl)amide (KHMDS) and [18]crown-6, whereas β-porphyrinylmethyl anions were highly unstable.
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku Kyoto, 606-8502, Japan.
authors.forename: Kenichi
authors.initials: K
authors.lastname: Kato
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic Systems and, Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
authors.forename: Woojae
authors.initials: W
authors.lastname: Kim
authors.affiliation: Spectroscopy Laboratory for Functional π-Electronic Systems and, Department of Chemistry, Yonsei University, Seoul, 120-749, Korea. dongho@yonsei.ac.kr.
authors.forename: Dongho
authors.initials: D
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku Kyoto, 606-8502, Japan. yori@kuchem.kyoto-u.ac.jp.
authors.forename: Hideki
authors.initials: H
authors.lastname: Yorimitsu
authors.affiliation: Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku Kyoto, 606-8502, Japan. osuka@kuchem.kyoto-u.ac.jp.
authors.forename: Atsuhiro
authors.initials: A
authors.lastname: Osuka
keywords: carbanions; carbocations; electronic structure; lithium; porphyrinoids