Diarylamine-Fused Subporphyrins

Proof of Twisted Intramolecular Charge Transfer (TICT) Mechanism

Koki Kise, Yongseok Hong, Norihito Fukui, Daiki Shimizu, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Diarylamine-fused subporphyrins 1 a and 1 b were synthesized from β,β-diiodo-meso-chloro subporphyrin 2 through a one-pot procedure involving nucleophilic aromatic substitution and SRN1-type intramolecular fusion reaction as the first example of meso-nitrogen-embedded subporphyrin. While non-fused counterparts 3 b and 4 b display effective fluorescence quenching due to twisted intramolecular charge transfer (TICT) in CH2Cl2 at room temperature, 1 b emits fluorescence with ΦF=0.18 under the same conditions, because conformational twisting is not allowed due to the fused structure. In addition, the oxidative titration with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave cation radical 7 for 1 a and cation radical and dication for 1 b. Actually, cation radical 7 was isolated through separation over silica gel column but was found to slowly decompose in concentrated solutions.

Original languageEnglish
Pages (from-to)8306-8310
Number of pages5
JournalChemistry - A European Journal
Volume24
Issue number33
DOIs
Publication statusPublished - 2018 Jun 12

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Cations
Charge transfer
Positive ions
Fluorescence
Silica Gel
Silica gel
Titration
Quenching
Substitution reactions
Nitrogen
Fusion reactions
Temperature
tris(4-bromophenyl)ammoniumyl hexachloroantimonate

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Kise, Koki ; Hong, Yongseok ; Fukui, Norihito ; Shimizu, Daiki ; Kim, Dongho ; Osuka, Atsuhiro. / Diarylamine-Fused Subporphyrins : Proof of Twisted Intramolecular Charge Transfer (TICT) Mechanism. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 33. pp. 8306-8310.
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Diarylamine-Fused Subporphyrins : Proof of Twisted Intramolecular Charge Transfer (TICT) Mechanism. / Kise, Koki; Hong, Yongseok; Fukui, Norihito; Shimizu, Daiki; Kim, Dongho; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 24, No. 33, 12.06.2018, p. 8306-8310.

Research output: Contribution to journalArticle

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AU - Kise, Koki

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