SiIV incorporation into a [28]hexaphyrin that triggered formation of möbius aromatic molecules

Shin Ichiro Ishida, Takayuki Tanaka, Jong Min Lim, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Incorporation of SiIV into an expanded porphyrin has been achieved for the first time. Treatment of [28]hexaphyrin 1 with CH 3SiCl3 and N,N-diisopropylethylamine gave SiIV complex 2 and its N-fused product 4 that both have Möbius aromatic nature. In both complexes, the coordinated Si atom is satisfied in a typical trigonal bipyramidal coordination. SiIV incorporation induces conformational rigidification and redshifted absorption profiles due to σ-π conjugation between the Si atom and hexaphyrin macrocycle. Tamao-Fleming oxidation of 2 with H2O2 gave β-hydroxy [28]hexaphyrin 5, which exists as a ruffled rectangular shape in the solid state, yet it has been revealed to exist predominantly as a twisted Möbius aromatic conformer in CH2Cl2.

Original languageEnglish
Pages (from-to)8274-8278
Number of pages5
JournalChemistry - A European Journal
Volume20
Issue number27
DOIs
Publication statusPublished - 2014 Jul 1

Fingerprint

Atoms
Molecules
Porphyrins
Oxidation
N,N-diisopropylethylamine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Ishida, Shin Ichiro ; Tanaka, Takayuki ; Lim, Jong Min ; Kim, Dongho ; Osuka, Atsuhiro. / SiIV incorporation into a [28]hexaphyrin that triggered formation of möbius aromatic molecules. In: Chemistry - A European Journal. 2014 ; Vol. 20, No. 27. pp. 8274-8278.
@article{5c0f895230d54d2ebb3e28087f356b5f,
title = "SiIV incorporation into a [28]hexaphyrin that triggered formation of m{\"o}bius aromatic molecules",
abstract = "Incorporation of SiIV into an expanded porphyrin has been achieved for the first time. Treatment of [28]hexaphyrin 1 with CH 3SiCl3 and N,N-diisopropylethylamine gave SiIV complex 2 and its N-fused product 4 that both have M{\"o}bius aromatic nature. In both complexes, the coordinated Si atom is satisfied in a typical trigonal bipyramidal coordination. SiIV incorporation induces conformational rigidification and redshifted absorption profiles due to σ-π conjugation between the Si atom and hexaphyrin macrocycle. Tamao-Fleming oxidation of 2 with H2O2 gave β-hydroxy [28]hexaphyrin 5, which exists as a ruffled rectangular shape in the solid state, yet it has been revealed to exist predominantly as a twisted M{\"o}bius aromatic conformer in CH2Cl2.",
author = "Ishida, {Shin Ichiro} and Takayuki Tanaka and Lim, {Jong Min} and Dongho Kim and Atsuhiro Osuka",
year = "2014",
month = "7",
day = "1",
doi = "10.1002/chem.201402929",
language = "English",
volume = "20",
pages = "8274--8278",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "27",

}

SiIV incorporation into a [28]hexaphyrin that triggered formation of möbius aromatic molecules. / Ishida, Shin Ichiro; Tanaka, Takayuki; Lim, Jong Min; Kim, Dongho; Osuka, Atsuhiro.

In: Chemistry - A European Journal, Vol. 20, No. 27, 01.07.2014, p. 8274-8278.

Research output: Contribution to journalArticle

TY - JOUR

T1 - SiIV incorporation into a [28]hexaphyrin that triggered formation of möbius aromatic molecules

AU - Ishida, Shin Ichiro

AU - Tanaka, Takayuki

AU - Lim, Jong Min

AU - Kim, Dongho

AU - Osuka, Atsuhiro

PY - 2014/7/1

Y1 - 2014/7/1

N2 - Incorporation of SiIV into an expanded porphyrin has been achieved for the first time. Treatment of [28]hexaphyrin 1 with CH 3SiCl3 and N,N-diisopropylethylamine gave SiIV complex 2 and its N-fused product 4 that both have Möbius aromatic nature. In both complexes, the coordinated Si atom is satisfied in a typical trigonal bipyramidal coordination. SiIV incorporation induces conformational rigidification and redshifted absorption profiles due to σ-π conjugation between the Si atom and hexaphyrin macrocycle. Tamao-Fleming oxidation of 2 with H2O2 gave β-hydroxy [28]hexaphyrin 5, which exists as a ruffled rectangular shape in the solid state, yet it has been revealed to exist predominantly as a twisted Möbius aromatic conformer in CH2Cl2.

AB - Incorporation of SiIV into an expanded porphyrin has been achieved for the first time. Treatment of [28]hexaphyrin 1 with CH 3SiCl3 and N,N-diisopropylethylamine gave SiIV complex 2 and its N-fused product 4 that both have Möbius aromatic nature. In both complexes, the coordinated Si atom is satisfied in a typical trigonal bipyramidal coordination. SiIV incorporation induces conformational rigidification and redshifted absorption profiles due to σ-π conjugation between the Si atom and hexaphyrin macrocycle. Tamao-Fleming oxidation of 2 with H2O2 gave β-hydroxy [28]hexaphyrin 5, which exists as a ruffled rectangular shape in the solid state, yet it has been revealed to exist predominantly as a twisted Möbius aromatic conformer in CH2Cl2.

UR - http://www.scopus.com/inward/record.url?scp=84903278325&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84903278325&partnerID=8YFLogxK

U2 - 10.1002/chem.201402929

DO - 10.1002/chem.201402929

M3 - Article

AN - SCOPUS:84903278325

VL - 20

SP - 8274

EP - 8278

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 27

ER -