Ferrocene-containing carbohydrate dendrimers

Peter R. Ashton, Vincenzo Balzani, Miguel Clemente-León, Barbara Colonna, Alberto Credi, Narayanaswamy Jayaraman, Francisco Raymo, J. Fraser Stoddart, Margherita Venturi

Research output: Contribution to journalArticle

97 Citations (Scopus)

Abstract

Aliphatic amines, incorporating one or three (branched) acylated β-D-glucopyranosyl residues, were coupled with the acid chloride of ferrocenecarboxylic acid and with the diacid chloride of 1,1′-ferrocenedicarboxylic acid to afford four dendrimer-type, carbohydrate-coated ferrocene derivatives in good yields (54-92%). Deprotection of the peracylated β-D-glucopyranosyl residues was achieved quantitatively by using Zemplén conditions, affording four water-soluble ferrocene derivatives. When only one of the two cyclopentadienyl rings of the ferrocene unit is substituted, strong complexes are formed with β-cyclodextrin in H2O, as demonstrated by liquid secondary ion mass spectrometry (LSIMS), 1H NMR spectroscopy, electrochemical measurements, and circular dichroism spectroscopy. Molecular dynamics calculations showed that the unsubstituted cyclopentadienyl ring is inserted through the cavity of the toroidal host in these complexes. The electrochemical behavior of the protected and deprotected ferrocene-containing dendrimers was investigated in acetonitrile and water, respectively. The diffusion coefficient decreases with increasing molecular weight of the compound. The potential for oxidation of the ferrocene core, the rate constant of heterogeneous electron transfer, and the rate constant for the energy-transfer reaction with the luminescent excited state of the [Ru(bpy)3]2+ complex (bpy=2,2′-bipyridine) are strongly affected by the number (one or two) of substituents and by the number (one or three) of carbohydrate branches present in the substituents. These effects are assigned to shielding of the ferrocene core by the dendritic branches. Electrochemical evidence for the existence of different conformers for one of the dendrimers in aqueous solution was obtained.

Original languageEnglish
Pages (from-to)673-684
Number of pages12
JournalChemistry - A European Journal
Volume8
Issue number3
DOIs
StatePublished - Feb 2 2002

Fingerprint

Dendrimers
Carbohydrates
Acids
Rate constants
Circular dichroism spectroscopy
Derivatives
Cyclodextrins
Secondary ion mass spectrometry
Acetonitrile
Excited states
Shielding
Energy transfer
Nuclear magnetic resonance spectroscopy
Molecular dynamics
Chlorides
Water
Amines
Molecular weight
Oxidation
Electrons

Keywords

  • Carbohydrates
  • Cyclodextrins
  • Dendrimers
  • Electrochemistry
  • Electron transfer
  • Ferrocenes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Ashton, P. R., Balzani, V., Clemente-León, M., Colonna, B., Credi, A., Jayaraman, N., ... Venturi, M. (2002). Ferrocene-containing carbohydrate dendrimers. Chemistry - A European Journal, 8(3), 673-684. https://doi.org/10.1002/1521-3765(20020201)8:3<673::AID-CHEM673>3.0.CO;2-D

Ferrocene-containing carbohydrate dendrimers. / Ashton, Peter R.; Balzani, Vincenzo; Clemente-León, Miguel; Colonna, Barbara; Credi, Alberto; Jayaraman, Narayanaswamy; Raymo, Francisco; Stoddart, J. Fraser; Venturi, Margherita.

In: Chemistry - A European Journal, Vol. 8, No. 3, 02.02.2002, p. 673-684.

Research output: Contribution to journalArticle

Ashton, PR, Balzani, V, Clemente-León, M, Colonna, B, Credi, A, Jayaraman, N, Raymo, F, Stoddart, JF & Venturi, M 2002, 'Ferrocene-containing carbohydrate dendrimers', Chemistry - A European Journal, vol. 8, no. 3, pp. 673-684. https://doi.org/10.1002/1521-3765(20020201)8:3<673::AID-CHEM673>3.0.CO;2-D
Ashton PR, Balzani V, Clemente-León M, Colonna B, Credi A, Jayaraman N et al. Ferrocene-containing carbohydrate dendrimers. Chemistry - A European Journal. 2002 Feb 2;8(3):673-684. https://doi.org/10.1002/1521-3765(20020201)8:3<673::AID-CHEM673>3.0.CO;2-D
Ashton, Peter R. ; Balzani, Vincenzo ; Clemente-León, Miguel ; Colonna, Barbara ; Credi, Alberto ; Jayaraman, Narayanaswamy ; Raymo, Francisco ; Stoddart, J. Fraser ; Venturi, Margherita. / Ferrocene-containing carbohydrate dendrimers. In: Chemistry - A European Journal. 2002 ; Vol. 8, No. 3. pp. 673-684.
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