Dual-mode "co-conformational" switching in catenanes incorporating bipyridinium and dialkylammonium recognition sites

Peter R. Ashton, Virna Baldoni, Vincenzo Balzani, Alberto Credi, H. D Andreas Hoffmann, Maria Victoria Martínez-Díaz, Francisco Raymo, J. Fraser Stoddart, Margherita Venturi

Research output: Contribution to journalArticle

82 Citations (Scopus)

Abstract

Three [2]catenanes and three [3]catenanes incorporating one or two π-electron-rich macrocyclic polyethers and one π-electron-deficient polycationic cyclophane have been synthesized in yields ranging from 4 to 38%. The π-electron-rich macrocyclic components possess either two 1,4-dioxybenzene or two 1,5-dioxynaphthalene recognition sites. The π-electron-deficient cyclophane components incorporate two bipyridinium and either one or two dialkylammonium recognition sites. The template-directed syntheses of these catenanes rely on i) π ··· π stacking interactions between the dioxyarene and bipyridinium recognition sites, ii) C-H ··· O hydrogen bonds between some of the bipyridinium hydrogen atoms and some of the polyether oxygen atoms, and iii) C-H ··· π interactions between some of the dioxyarene hydrogen atoms and the aromatic spacers separating the bipyridinium units. The six catenanes were characterized by mass spectrometry and by both 1H and 13C NMR spectroscopy. The absorption spectra and the electrochemical properties of the catenanes have been investigated and compared with those exhibited by the component macrocycles and by related known catenanes. Broad and weak absorption bands in the visible region, originating from charge-transfer (CT) interactions between electron-donor and electron-acceptor units, have been observed. Such charge-transfer interactions are responsible for the quenching of the potentially fluorescent excited states of the aromatic units of the macrocyclic polyether components. The redox behavior of these novel compounds has been investigated and correlations among the observed redox potentials are illustrated and discussed. The catenanes undergo co-conformational switching upon one-electron reduction of the two bipyridinium units. One of them - in its reduced form - can be also switched by acid/base inputs and exhibits AND logic behavior. The co-conformational rearrangements induced by the redox and acid/base stimulations lend themselves to exploitation in the development of molecular-level machines and logic gates.

Original languageEnglish
Pages (from-to)3482-3493
Number of pages12
JournalChemistry - A European Journal
Volume7
Issue number16
DOIs
StatePublished - Aug 17 2001

Fingerprint

Catenanes
Electrons
Polyethers
Atoms
Hydrogen
Charge transfer
Absorption spectra
Acids
Logic gates
Electrochemical properties
Excited states
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Quenching
Hydrogen bonds
Oxygen

Keywords

  • Catenanes
  • Cyclophanes
  • Electrochemistry
  • Molecular machines
  • Template synthesis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Dual-mode "co-conformational" switching in catenanes incorporating bipyridinium and dialkylammonium recognition sites. / Ashton, Peter R.; Baldoni, Virna; Balzani, Vincenzo; Credi, Alberto; Hoffmann, H. D Andreas; Martínez-Díaz, Maria Victoria; Raymo, Francisco; Stoddart, J. Fraser; Venturi, Margherita.

In: Chemistry - A European Journal, Vol. 7, No. 16, 17.08.2001, p. 3482-3493.

Research output: Contribution to journalArticle

Ashton, Peter R. ; Baldoni, Virna ; Balzani, Vincenzo ; Credi, Alberto ; Hoffmann, H. D Andreas ; Martínez-Díaz, Maria Victoria ; Raymo, Francisco ; Stoddart, J. Fraser ; Venturi, Margherita. / Dual-mode "co-conformational" switching in catenanes incorporating bipyridinium and dialkylammonium recognition sites. In: Chemistry - A European Journal. 2001 ; Vol. 7, No. 16. pp. 3482-3493.
@article{e74e9e873d464c79b68f9f72e8c5f52d,
title = "Dual-mode {"}co-conformational{"} switching in catenanes incorporating bipyridinium and dialkylammonium recognition sites",
abstract = "Three [2]catenanes and three [3]catenanes incorporating one or two π-electron-rich macrocyclic polyethers and one π-electron-deficient polycationic cyclophane have been synthesized in yields ranging from 4 to 38{\%}. The π-electron-rich macrocyclic components possess either two 1,4-dioxybenzene or two 1,5-dioxynaphthalene recognition sites. The π-electron-deficient cyclophane components incorporate two bipyridinium and either one or two dialkylammonium recognition sites. The template-directed syntheses of these catenanes rely on i) π ··· π stacking interactions between the dioxyarene and bipyridinium recognition sites, ii) C-H ··· O hydrogen bonds between some of the bipyridinium hydrogen atoms and some of the polyether oxygen atoms, and iii) C-H ··· π interactions between some of the dioxyarene hydrogen atoms and the aromatic spacers separating the bipyridinium units. The six catenanes were characterized by mass spectrometry and by both 1H and 13C NMR spectroscopy. The absorption spectra and the electrochemical properties of the catenanes have been investigated and compared with those exhibited by the component macrocycles and by related known catenanes. Broad and weak absorption bands in the visible region, originating from charge-transfer (CT) interactions between electron-donor and electron-acceptor units, have been observed. Such charge-transfer interactions are responsible for the quenching of the potentially fluorescent excited states of the aromatic units of the macrocyclic polyether components. The redox behavior of these novel compounds has been investigated and correlations among the observed redox potentials are illustrated and discussed. The catenanes undergo co-conformational switching upon one-electron reduction of the two bipyridinium units. One of them - in its reduced form - can be also switched by acid/base inputs and exhibits AND logic behavior. The co-conformational rearrangements induced by the redox and acid/base stimulations lend themselves to exploitation in the development of molecular-level machines and logic gates.",
keywords = "Catenanes, Cyclophanes, Electrochemistry, Molecular machines, Template synthesis",
author = "Ashton, {Peter R.} and Virna Baldoni and Vincenzo Balzani and Alberto Credi and Hoffmann, {H. D Andreas} and Mart{\'i}nez-D{\'i}az, {Maria Victoria} and Francisco Raymo and Stoddart, {J. Fraser} and Margherita Venturi",
year = "2001",
month = "8",
day = "17",
doi = "10.1002/1521-3765(20010817)7:16<3482::AID-CHEM3482>3.0.CO;2-G",
language = "English",
volume = "7",
pages = "3482--3493",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "16",

}

TY - JOUR

T1 - Dual-mode "co-conformational" switching in catenanes incorporating bipyridinium and dialkylammonium recognition sites

AU - Ashton, Peter R.

AU - Baldoni, Virna

AU - Balzani, Vincenzo

AU - Credi, Alberto

AU - Hoffmann, H. D Andreas

AU - Martínez-Díaz, Maria Victoria

AU - Raymo, Francisco

AU - Stoddart, J. Fraser

AU - Venturi, Margherita

PY - 2001/8/17

Y1 - 2001/8/17

N2 - Three [2]catenanes and three [3]catenanes incorporating one or two π-electron-rich macrocyclic polyethers and one π-electron-deficient polycationic cyclophane have been synthesized in yields ranging from 4 to 38%. The π-electron-rich macrocyclic components possess either two 1,4-dioxybenzene or two 1,5-dioxynaphthalene recognition sites. The π-electron-deficient cyclophane components incorporate two bipyridinium and either one or two dialkylammonium recognition sites. The template-directed syntheses of these catenanes rely on i) π ··· π stacking interactions between the dioxyarene and bipyridinium recognition sites, ii) C-H ··· O hydrogen bonds between some of the bipyridinium hydrogen atoms and some of the polyether oxygen atoms, and iii) C-H ··· π interactions between some of the dioxyarene hydrogen atoms and the aromatic spacers separating the bipyridinium units. The six catenanes were characterized by mass spectrometry and by both 1H and 13C NMR spectroscopy. The absorption spectra and the electrochemical properties of the catenanes have been investigated and compared with those exhibited by the component macrocycles and by related known catenanes. Broad and weak absorption bands in the visible region, originating from charge-transfer (CT) interactions between electron-donor and electron-acceptor units, have been observed. Such charge-transfer interactions are responsible for the quenching of the potentially fluorescent excited states of the aromatic units of the macrocyclic polyether components. The redox behavior of these novel compounds has been investigated and correlations among the observed redox potentials are illustrated and discussed. The catenanes undergo co-conformational switching upon one-electron reduction of the two bipyridinium units. One of them - in its reduced form - can be also switched by acid/base inputs and exhibits AND logic behavior. The co-conformational rearrangements induced by the redox and acid/base stimulations lend themselves to exploitation in the development of molecular-level machines and logic gates.

AB - Three [2]catenanes and three [3]catenanes incorporating one or two π-electron-rich macrocyclic polyethers and one π-electron-deficient polycationic cyclophane have been synthesized in yields ranging from 4 to 38%. The π-electron-rich macrocyclic components possess either two 1,4-dioxybenzene or two 1,5-dioxynaphthalene recognition sites. The π-electron-deficient cyclophane components incorporate two bipyridinium and either one or two dialkylammonium recognition sites. The template-directed syntheses of these catenanes rely on i) π ··· π stacking interactions between the dioxyarene and bipyridinium recognition sites, ii) C-H ··· O hydrogen bonds between some of the bipyridinium hydrogen atoms and some of the polyether oxygen atoms, and iii) C-H ··· π interactions between some of the dioxyarene hydrogen atoms and the aromatic spacers separating the bipyridinium units. The six catenanes were characterized by mass spectrometry and by both 1H and 13C NMR spectroscopy. The absorption spectra and the electrochemical properties of the catenanes have been investigated and compared with those exhibited by the component macrocycles and by related known catenanes. Broad and weak absorption bands in the visible region, originating from charge-transfer (CT) interactions between electron-donor and electron-acceptor units, have been observed. Such charge-transfer interactions are responsible for the quenching of the potentially fluorescent excited states of the aromatic units of the macrocyclic polyether components. The redox behavior of these novel compounds has been investigated and correlations among the observed redox potentials are illustrated and discussed. The catenanes undergo co-conformational switching upon one-electron reduction of the two bipyridinium units. One of them - in its reduced form - can be also switched by acid/base inputs and exhibits AND logic behavior. The co-conformational rearrangements induced by the redox and acid/base stimulations lend themselves to exploitation in the development of molecular-level machines and logic gates.

KW - Catenanes

KW - Cyclophanes

KW - Electrochemistry

KW - Molecular machines

KW - Template synthesis

UR - http://www.scopus.com/inward/record.url?scp=0035902771&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035902771&partnerID=8YFLogxK

U2 - 10.1002/1521-3765(20010817)7:16<3482::AID-CHEM3482>3.0.CO;2-G

DO - 10.1002/1521-3765(20010817)7:16<3482::AID-CHEM3482>3.0.CO;2-G

M3 - Article

C2 - 11560318

AN - SCOPUS:0035902771

VL - 7

SP - 3482

EP - 3493

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 16

ER -