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Article: Ferrocene-containing carbohydrate dendrimers

TitleFerrocene-containing carbohydrate dendrimers
Authors
KeywordsCarbohydrates
Cyclodextrins
Dendrimers
Electrochemistry
Electron transfer
Ferrocenes
Issue Date2002
Citation
Chemistry - A European Journal, 2002, v. 8, n. 3, p. 673-684 How to Cite?
AbstractAliphatic 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.
Persistent Identifierhttp://hdl.handle.net/10722/332512
ISSN
2023 Impact Factor: 3.9
2023 SCImago Journal Rankings: 1.058
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorAshton, Peter R.-
dc.contributor.authorBalzani, Vincenzo-
dc.contributor.authorClemente-León, Miguel-
dc.contributor.authorColonna, Barbara-
dc.contributor.authorCredi, Alberto-
dc.contributor.authorJayaraman, Narayanaswamy-
dc.contributor.authorRaymo, Françisco M.-
dc.contributor.authorStoddart, J. Fraser-
dc.contributor.authorVenturi, Margherita-
dc.date.accessioned2023-10-06T05:12:06Z-
dc.date.available2023-10-06T05:12:06Z-
dc.date.issued2002-
dc.identifier.citationChemistry - A European Journal, 2002, v. 8, n. 3, p. 673-684-
dc.identifier.issn0947-6539-
dc.identifier.urihttp://hdl.handle.net/10722/332512-
dc.description.abstractAliphatic 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.-
dc.languageeng-
dc.relation.ispartofChemistry - A European Journal-
dc.subjectCarbohydrates-
dc.subjectCyclodextrins-
dc.subjectDendrimers-
dc.subjectElectrochemistry-
dc.subjectElectron transfer-
dc.subjectFerrocenes-
dc.titleFerrocene-containing carbohydrate dendrimers-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/1521-3765(20020201)8:3<673::AID-CHEM673>3.0.CO;2-D-
dc.identifier.pmid11855715-
dc.identifier.scopuseid_2-s2.0-0037006232-
dc.identifier.volume8-
dc.identifier.issue3-
dc.identifier.spage673-
dc.identifier.epage684-
dc.identifier.isiWOS:000173750300014-

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