Molecular recognition of chiral diporphyrin receptor with a macrocyclic cavity for intercalation of aromatic compounds

Tadashi Ema, Norichika Ura, Katsuya Eguchi, Takashi Sakai

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Chiral diporphyrin receptor 1, which has a macrocyclic cavity for the intercalation of aromatic guest molecules, was designed and synthesized from pyrrole in five steps. The binding constants (Ka) revealed the greater affinity of 1 for more electron-deficient aromatic guests. The complexation between 1 and 1,3,5-trinitrobenzene (G8) (Ka = 1850M -1) was much stronger than that between porphyrin monomer 3 and G8 (Ka = 50M -1). This result strongly suggests that G8 was intercalated into the cavity of 1 via cooperative double π-π stacking. Interestingly, 1 enabled the naked-eye detection of an aromatic explosive G8; a dark-red solution of 1 in CHCl3 turned into a colloidal suspension upon addition of G8, and the light was scattered. Fluorescence spectroscopy was also useful for the selective detection of G8; fluorescence of 1 was quenched by complexation with G8, which was visible with the naked eye. Despite modest binding constants for dinitrobenzene derivatives, 1 showed a good ability to discriminate the enantiomers of twelve chiral compounds bearing a dinitrophenyl group by NMR spectroscopy. The MM calculations with the MM3 force field reproduced inclusion complexes between 1 and nitroaromatic compounds. The mechanism of chiral discrimination is proposed.

Original languageEnglish
Pages (from-to)101-109
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume85
Issue number1
DOIs
Publication statusPublished - 2012

Fingerprint

Molecular recognition
Aromatic compounds
Intercalation
Complexation
Bearings (structural)
Dinitrobenzenes
Pyrroles
Enantiomers
Porphyrins
Fluorescence spectroscopy
Nuclear magnetic resonance spectroscopy
Suspensions
Monomers
Fluorescence
Derivatives
Molecules
Electrons
chiral diporphyrin receptor 1
sym-trinitrobenzene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Molecular recognition of chiral diporphyrin receptor with a macrocyclic cavity for intercalation of aromatic compounds. / Ema, Tadashi; Ura, Norichika; Eguchi, Katsuya; Sakai, Takashi.

In: Bulletin of the Chemical Society of Japan, Vol. 85, No. 1, 2012, p. 101-109.

Research output: Contribution to journalArticle

@article{3aab6700f6e84b3cac333db6d4e122da,
title = "Molecular recognition of chiral diporphyrin receptor with a macrocyclic cavity for intercalation of aromatic compounds",
abstract = "Chiral diporphyrin receptor 1, which has a macrocyclic cavity for the intercalation of aromatic guest molecules, was designed and synthesized from pyrrole in five steps. The binding constants (Ka) revealed the greater affinity of 1 for more electron-deficient aromatic guests. The complexation between 1 and 1,3,5-trinitrobenzene (G8) (Ka = 1850M -1) was much stronger than that between porphyrin monomer 3 and G8 (Ka = 50M -1). This result strongly suggests that G8 was intercalated into the cavity of 1 via cooperative double π-π stacking. Interestingly, 1 enabled the naked-eye detection of an aromatic explosive G8; a dark-red solution of 1 in CHCl3 turned into a colloidal suspension upon addition of G8, and the light was scattered. Fluorescence spectroscopy was also useful for the selective detection of G8; fluorescence of 1 was quenched by complexation with G8, which was visible with the naked eye. Despite modest binding constants for dinitrobenzene derivatives, 1 showed a good ability to discriminate the enantiomers of twelve chiral compounds bearing a dinitrophenyl group by NMR spectroscopy. The MM calculations with the MM3 force field reproduced inclusion complexes between 1 and nitroaromatic compounds. The mechanism of chiral discrimination is proposed.",
author = "Tadashi Ema and Norichika Ura and Katsuya Eguchi and Takashi Sakai",
year = "2012",
doi = "10.1246/bcsj.20110230",
language = "English",
volume = "85",
pages = "101--109",
journal = "Bulletin of the Chemical Society of Japan",
issn = "0009-2673",
publisher = "Chemical Society of Japan",
number = "1",

}

TY - JOUR

T1 - Molecular recognition of chiral diporphyrin receptor with a macrocyclic cavity for intercalation of aromatic compounds

AU - Ema, Tadashi

AU - Ura, Norichika

AU - Eguchi, Katsuya

AU - Sakai, Takashi

PY - 2012

Y1 - 2012

N2 - Chiral diporphyrin receptor 1, which has a macrocyclic cavity for the intercalation of aromatic guest molecules, was designed and synthesized from pyrrole in five steps. The binding constants (Ka) revealed the greater affinity of 1 for more electron-deficient aromatic guests. The complexation between 1 and 1,3,5-trinitrobenzene (G8) (Ka = 1850M -1) was much stronger than that between porphyrin monomer 3 and G8 (Ka = 50M -1). This result strongly suggests that G8 was intercalated into the cavity of 1 via cooperative double π-π stacking. Interestingly, 1 enabled the naked-eye detection of an aromatic explosive G8; a dark-red solution of 1 in CHCl3 turned into a colloidal suspension upon addition of G8, and the light was scattered. Fluorescence spectroscopy was also useful for the selective detection of G8; fluorescence of 1 was quenched by complexation with G8, which was visible with the naked eye. Despite modest binding constants for dinitrobenzene derivatives, 1 showed a good ability to discriminate the enantiomers of twelve chiral compounds bearing a dinitrophenyl group by NMR spectroscopy. The MM calculations with the MM3 force field reproduced inclusion complexes between 1 and nitroaromatic compounds. The mechanism of chiral discrimination is proposed.

AB - Chiral diporphyrin receptor 1, which has a macrocyclic cavity for the intercalation of aromatic guest molecules, was designed and synthesized from pyrrole in five steps. The binding constants (Ka) revealed the greater affinity of 1 for more electron-deficient aromatic guests. The complexation between 1 and 1,3,5-trinitrobenzene (G8) (Ka = 1850M -1) was much stronger than that between porphyrin monomer 3 and G8 (Ka = 50M -1). This result strongly suggests that G8 was intercalated into the cavity of 1 via cooperative double π-π stacking. Interestingly, 1 enabled the naked-eye detection of an aromatic explosive G8; a dark-red solution of 1 in CHCl3 turned into a colloidal suspension upon addition of G8, and the light was scattered. Fluorescence spectroscopy was also useful for the selective detection of G8; fluorescence of 1 was quenched by complexation with G8, which was visible with the naked eye. Despite modest binding constants for dinitrobenzene derivatives, 1 showed a good ability to discriminate the enantiomers of twelve chiral compounds bearing a dinitrophenyl group by NMR spectroscopy. The MM calculations with the MM3 force field reproduced inclusion complexes between 1 and nitroaromatic compounds. The mechanism of chiral discrimination is proposed.

UR - http://www.scopus.com/inward/record.url?scp=84856002678&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84856002678&partnerID=8YFLogxK

U2 - 10.1246/bcsj.20110230

DO - 10.1246/bcsj.20110230

M3 - Article

AN - SCOPUS:84856002678

VL - 85

SP - 101

EP - 109

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 1

ER -