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 language | English |
|---|---|
| Pages (from-to) | 1947-1956 |
| Number of pages | 10 |
| Journal | Journal of Organic Chemistry |
| Volume | 65 |
| Issue number | 7 |
| DOIs | |
| State | Published - Apr 7 2000 |
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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 journal › Article
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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.
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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 -