title: Site-specific installation and study of electroactive units in every layer of dendrons.
abstract: Whereas encapsulation of functional groups at the core of dendrimers is well-understood, very little is known about their intermediate layers or even the periphery. Here we report on a systematic investigation of every layer of dendrimers by incorporating a single ferrocene unit in well-defined locations in dendrons. Site-specific incorporation of the ferrocene unit was achieved by utilizing the dendrimer sequencing methodology. We show here that the redox potential values of ferrocene at intermediate layers were remarkably different from those at the core and the periphery. Although redox potential values were location-dependent, no significant change in the rate of heterogeneous electron transfer (k(0)) was observed with respect to locations. This was attributed to the possibility that free rotation of dendrimer nullifies the distance between the electrode and ferrocene unit. Finally, we also show that no Faradaic current was observed for the amphiphilic assemblies of these dendrons, whereas the same dendron did exhibit significant Faradaic current in nonassembling solvent environments.
authors.affiliation: Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, USA.
authors.forename: Malar A
authors.initials: MA
authors.lastname: Azagarsamy
authors.forename: Kothandam
authors.initials: K
authors.lastname: Krishnamoorthy
authors.forename: Kulandaivelu
authors.initials: K
authors.lastname: Sivanandan
authors.forename: S
authors.initials: S
authors.lastname: Thayumanavan
mesh_terms: D050091:Dendrimers / Q000138:chemical synthesis / Q000737:chemistry*; D004563:Electrochemistry; D004566:Electrodes; D004579:Electron Transport; D005296:Ferrous Compounds / Q000737:chemistry*; D000075163:Metallocenes; D010084:Oxidation-Reduction; D012997:Solvents / Q000737:chemistry
chemical_list: D050091:Dendrimers; D005296:Ferrous Compounds; D000075163:Metallocenes; D012997:Solvents; C004998:ferrocene