The electrochemically-driven decomplexation/recomplexation of inclusion adducts of ferrocene derivatives with an electron-accepting receptor

Vincenzo Balzani, Jan Becher, Alberto Credi, Mogens B. Nielsen, Francisco Raymo, J. Fraser Stoddart, Anna Maria Talarico, Margherita Venturi

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), binds 1,1'-disubstituted ferrocene-based polyethers as a result of (i) [π···π] stacking between the π-electron-deficient bipyridinium units and the π- electron-rich cyclopentadienyl rings and (ii) [C-H···O] hydrogen bonds between the α-bipyridinium hydrogen atoms and the polyether oxygen atoms. However, even the presence of a bulky tetraarylmethane group - which is too large to thread through the cavity of the cyclophane host - at the end of each of the two polyether substituents of the ferrocene-containing guest does not discourage adduct formation of the inclusion type. Thus, in these adducts, the ferrocene unit of the guest is located inside the cavity of the host with its two polyether chains protruding outward from the same side of the host. The alternative pseudorotaxane geometry is not observed in solutions of these 1:1 adducts. The host - guest adducts display absorption bands in the visible spectral region, characteristic of charge-transfer interactions. In the case of one of these adducts, reversible decomplexation/recomplexation takes place upon electrochemical oxidation/reduction of the ferrocene-based unit or upon reduction/oxidation of the tetracationic cyclophane.

Original languageEnglish
Pages (from-to)1947-1956
Number of pages10
JournalJournal of Organic Chemistry
Volume65
Issue number7
DOIs
StatePublished - Apr 7 2000

Fingerprint

Polyethers
Derivatives
Electrons
Rotaxanes
Atoms
Paraquat
Electrochemical oxidation
Charge transfer
Absorption spectra
Hydrogen
Hydrogen bonds
Oxygen
Oxidation
Geometry
ferrocene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

The electrochemically-driven decomplexation/recomplexation of inclusion adducts of ferrocene derivatives with an electron-accepting receptor. / Balzani, Vincenzo; Becher, Jan; Credi, Alberto; Nielsen, Mogens B.; Raymo, Francisco; Stoddart, J. Fraser; Talarico, Anna Maria; Venturi, Margherita.

In: Journal of Organic Chemistry, Vol. 65, No. 7, 07.04.2000, p. 1947-1956.

Research output: Contribution to journalArticle

Balzani, Vincenzo ; Becher, Jan ; Credi, Alberto ; Nielsen, Mogens B. ; Raymo, Francisco ; Stoddart, J. Fraser ; Talarico, Anna Maria ; Venturi, Margherita. / The electrochemically-driven decomplexation/recomplexation of inclusion adducts of ferrocene derivatives with an electron-accepting receptor. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 7. pp. 1947-1956.
@article{8aa52b365ae54ce6a58cefe1c2c7d37c,
title = "The electrochemically-driven decomplexation/recomplexation of inclusion adducts of ferrocene derivatives with an electron-accepting receptor",
abstract = "The tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), binds 1,1'-disubstituted ferrocene-based polyethers as a result of (i) [π···π] stacking between the π-electron-deficient bipyridinium units and the π- electron-rich cyclopentadienyl rings and (ii) [C-H···O] hydrogen bonds between the α-bipyridinium hydrogen atoms and the polyether oxygen atoms. However, even the presence of a bulky tetraarylmethane group - which is too large to thread through the cavity of the cyclophane host - at the end of each of the two polyether substituents of the ferrocene-containing guest does not discourage adduct formation of the inclusion type. Thus, in these adducts, the ferrocene unit of the guest is located inside the cavity of the host with its two polyether chains protruding outward from the same side of the host. The alternative pseudorotaxane geometry is not observed in solutions of these 1:1 adducts. The host - guest adducts display absorption bands in the visible spectral region, characteristic of charge-transfer interactions. In the case of one of these adducts, reversible decomplexation/recomplexation takes place upon electrochemical oxidation/reduction of the ferrocene-based unit or upon reduction/oxidation of the tetracationic cyclophane.",
author = "Vincenzo Balzani and Jan Becher and Alberto Credi and Nielsen, {Mogens B.} and Francisco Raymo and Stoddart, {J. Fraser} and Talarico, {Anna Maria} and Margherita Venturi",
year = "2000",
month = "4",
day = "7",
doi = "10.1021/jo991467z",
language = "English",
volume = "65",
pages = "1947--1956",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "7",

}

TY - JOUR

T1 - The electrochemically-driven decomplexation/recomplexation of inclusion adducts of ferrocene derivatives with an electron-accepting receptor

AU - Balzani, Vincenzo

AU - Becher, Jan

AU - Credi, Alberto

AU - Nielsen, Mogens B.

AU - Raymo, Francisco

AU - Stoddart, J. Fraser

AU - Talarico, Anna Maria

AU - Venturi, Margherita

PY - 2000/4/7

Y1 - 2000/4/7

N2 - The tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), binds 1,1'-disubstituted ferrocene-based polyethers as a result of (i) [π···π] stacking between the π-electron-deficient bipyridinium units and the π- electron-rich cyclopentadienyl rings and (ii) [C-H···O] hydrogen bonds between the α-bipyridinium hydrogen atoms and the polyether oxygen atoms. However, even the presence of a bulky tetraarylmethane group - which is too large to thread through the cavity of the cyclophane host - at the end of each of the two polyether substituents of the ferrocene-containing guest does not discourage adduct formation of the inclusion type. Thus, in these adducts, the ferrocene unit of the guest is located inside the cavity of the host with its two polyether chains protruding outward from the same side of the host. The alternative pseudorotaxane geometry is not observed in solutions of these 1:1 adducts. The host - guest adducts display absorption bands in the visible spectral region, characteristic of charge-transfer interactions. In the case of one of these adducts, reversible decomplexation/recomplexation takes place upon electrochemical oxidation/reduction of the ferrocene-based unit or upon reduction/oxidation of the tetracationic cyclophane.

AB - The tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), binds 1,1'-disubstituted ferrocene-based polyethers as a result of (i) [π···π] stacking between the π-electron-deficient bipyridinium units and the π- electron-rich cyclopentadienyl rings and (ii) [C-H···O] hydrogen bonds between the α-bipyridinium hydrogen atoms and the polyether oxygen atoms. However, even the presence of a bulky tetraarylmethane group - which is too large to thread through the cavity of the cyclophane host - at the end of each of the two polyether substituents of the ferrocene-containing guest does not discourage adduct formation of the inclusion type. Thus, in these adducts, the ferrocene unit of the guest is located inside the cavity of the host with its two polyether chains protruding outward from the same side of the host. The alternative pseudorotaxane geometry is not observed in solutions of these 1:1 adducts. The host - guest adducts display absorption bands in the visible spectral region, characteristic of charge-transfer interactions. In the case of one of these adducts, reversible decomplexation/recomplexation takes place upon electrochemical oxidation/reduction of the ferrocene-based unit or upon reduction/oxidation of the tetracationic cyclophane.

UR - http://www.scopus.com/inward/record.url?scp=0034616371&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034616371&partnerID=8YFLogxK

U2 - 10.1021/jo991467z

DO - 10.1021/jo991467z

M3 - Article

AN - SCOPUS:0034616371

VL - 65

SP - 1947

EP - 1956

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 7

ER -