Issue 17, 2006

Electrochemical studies of porphyrin-appended dendrimers

Abstract

The electrochemical properties of porphyrin-appended dendrimers containing 2-, 4-, 8-, 16-, 32- and 64-porphyrin macrocycles in their free-base and zinc(II) forms have been investigated. Both series gave diffusional based voltammetric responses in dichloromethane. There was minimal effect of dendrimer generation on the redox potentials. Multiple π-cation and anion radicals as well as dications and dianions were formed on the surface of the dendrimers on oxidation or reduction as appropriate, with each cyclic voltammetric wave representing electron transfer to or from multiple non-interacting porphyrin sites. Electrostatic interactions in the higher generation dendrimers result in kinetic effects being observed for the highly charged species generated when each porphyrin unit is doubly or triply oxidised. The number of electrons transferred on reduction or oxidation of the dendrimers was evaluated using steady-state microelectrode voltammetry. For the lower generations of species a good correlation was observed between numbers of electrons transferred and number of porphyrin entities per molecule; for the dendrimers containing 32 and 64 units, however, slight negative deviations were observed, possibly due to electrostatic interactions as the porphyrins become closer packed.

Graphical abstract: Electrochemical studies of porphyrin-appended dendrimers

Article information

Article type
Paper
Submitted
16 Nov 2005
Accepted
23 Feb 2006
First published
24 Mar 2006

Phys. Chem. Chem. Phys., 2006,8, 2058-2065

Electrochemical studies of porphyrin-appended dendrimers

C. F. Hogan, A. R. Harris, A. M. Bond, J. Sly and M. J. Crossley, Phys. Chem. Chem. Phys., 2006, 8, 2058 DOI: 10.1039/B516281E

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