Meso-hydroxysubporphyrins: A cyclic trimeric assembly and a stable meso-Oxy radical

Daiki Shimizu, Juwon Oh, Ko Furukawa, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Treatment of meso-chlorosubporphyrin with potassium hydroxide in DMSO followed by aqueous work up and recrystallization gave a cyclic trimer consisting of meso-hydroxysubporphyrin units linked between the central boron atoms and meso-hydroxy groups. Solutions of this trimer are nonfluorescent, but become fluorescent when exposed to acid or base, since hydrolytic cleavage of the axial B-O bonds generates the meso-hydroxysubporphyrin monomer or its oxyanion. Ring cleavage of the trimer was also effected by reaction with phenylmagnesium bromide to produce meso-hydroxy-B-phenyl subporphyrin, which can be quantitatively oxidized with PbO2 to furnish a subporphyrin meso-oxy radical as a remarkably stable species as a result of spin delocalization over almost the entire molecule.

Original languageEnglish
Pages (from-to)6613-6617
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number22
DOIs
Publication statusPublished - 2015 May 1

Fingerprint

Potassium hydroxide
Boron
Dimethyl Sulfoxide
Bromides
Monomers
Atoms
Molecules
Acids
potassium hydroxide

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Shimizu, Daiki ; Oh, Juwon ; Furukawa, Ko ; Kim, Dongho ; Osuka, Atsuhiro. / Meso-hydroxysubporphyrins : A cyclic trimeric assembly and a stable meso-Oxy radical. In: Angewandte Chemie - International Edition. 2015 ; Vol. 54, No. 22. pp. 6613-6617.
@article{5a4700f2dc4c4589b2979545b188f0c5,
title = "Meso-hydroxysubporphyrins: A cyclic trimeric assembly and a stable meso-Oxy radical",
abstract = "Treatment of meso-chlorosubporphyrin with potassium hydroxide in DMSO followed by aqueous work up and recrystallization gave a cyclic trimer consisting of meso-hydroxysubporphyrin units linked between the central boron atoms and meso-hydroxy groups. Solutions of this trimer are nonfluorescent, but become fluorescent when exposed to acid or base, since hydrolytic cleavage of the axial B-O bonds generates the meso-hydroxysubporphyrin monomer or its oxyanion. Ring cleavage of the trimer was also effected by reaction with phenylmagnesium bromide to produce meso-hydroxy-B-phenyl subporphyrin, which can be quantitatively oxidized with PbO2 to furnish a subporphyrin meso-oxy radical as a remarkably stable species as a result of spin delocalization over almost the entire molecule.",
author = "Daiki Shimizu and Juwon Oh and Ko Furukawa and Dongho Kim and Atsuhiro Osuka",
year = "2015",
month = "5",
day = "1",
doi = "10.1002/anie.201501592",
language = "English",
volume = "54",
pages = "6613--6617",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "22",

}

Meso-hydroxysubporphyrins : A cyclic trimeric assembly and a stable meso-Oxy radical. / Shimizu, Daiki; Oh, Juwon; Furukawa, Ko; Kim, Dongho; Osuka, Atsuhiro.

In: Angewandte Chemie - International Edition, Vol. 54, No. 22, 01.05.2015, p. 6613-6617.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Meso-hydroxysubporphyrins

T2 - A cyclic trimeric assembly and a stable meso-Oxy radical

AU - Shimizu, Daiki

AU - Oh, Juwon

AU - Furukawa, Ko

AU - Kim, Dongho

AU - Osuka, Atsuhiro

PY - 2015/5/1

Y1 - 2015/5/1

N2 - Treatment of meso-chlorosubporphyrin with potassium hydroxide in DMSO followed by aqueous work up and recrystallization gave a cyclic trimer consisting of meso-hydroxysubporphyrin units linked between the central boron atoms and meso-hydroxy groups. Solutions of this trimer are nonfluorescent, but become fluorescent when exposed to acid or base, since hydrolytic cleavage of the axial B-O bonds generates the meso-hydroxysubporphyrin monomer or its oxyanion. Ring cleavage of the trimer was also effected by reaction with phenylmagnesium bromide to produce meso-hydroxy-B-phenyl subporphyrin, which can be quantitatively oxidized with PbO2 to furnish a subporphyrin meso-oxy radical as a remarkably stable species as a result of spin delocalization over almost the entire molecule.

AB - Treatment of meso-chlorosubporphyrin with potassium hydroxide in DMSO followed by aqueous work up and recrystallization gave a cyclic trimer consisting of meso-hydroxysubporphyrin units linked between the central boron atoms and meso-hydroxy groups. Solutions of this trimer are nonfluorescent, but become fluorescent when exposed to acid or base, since hydrolytic cleavage of the axial B-O bonds generates the meso-hydroxysubporphyrin monomer or its oxyanion. Ring cleavage of the trimer was also effected by reaction with phenylmagnesium bromide to produce meso-hydroxy-B-phenyl subporphyrin, which can be quantitatively oxidized with PbO2 to furnish a subporphyrin meso-oxy radical as a remarkably stable species as a result of spin delocalization over almost the entire molecule.

UR - http://www.scopus.com/inward/record.url?scp=84930201873&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84930201873&partnerID=8YFLogxK

U2 - 10.1002/anie.201501592

DO - 10.1002/anie.201501592

M3 - Article

C2 - 25864562

AN - SCOPUS:84930201873

VL - 54

SP - 6613

EP - 6617

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 22

ER -