Polyelectrolytes as interfaces for retarding back-reaction in photoinduced electron transfer
Flash photolysis experiments on the effect of the polyelectrolytes poly(styrene sulfonate) (PSS) and Poly(N,N-dimethyl-3, 5-dimethylene piperidinium chloride) (PolyP) on the photoinduced electron transfer reaction between zinc(II) tetrakis (4-N-methylpyridinium)porphyin (ZnP) and propyl viologen sulfonate (PVS/sup 0/) show that PSS decreases both the forward and back- electron transfer reaction rates significantly, by a factor of approx. 60. The effect of PSS is due to hydrophobic envelopment of ZnP by the polyelectrolyte, hindering approach of reactants to it and thus reducing all bimolecular reaction rates between ZnP and species in solution. The cationic polyelectrolyte, PolyP, decreases the back-electron transfer rate by a factor of approx. 2 without affecting other bimolecular reaction rates. This effect is probably due to binding of the PVS/sup -/ to the polyelectrolyte, which then repels the oxidized porphyrin electrostatically.
- Research Organization:
- Lawrence Berkeley Lab., CA (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6454504
- Report Number(s):
- LBL-18290; CONF-8409141-1; ON: DE85000713
- Resource Relation:
- Photochemistry of metal complexes conference, Tokyo, Japan, 2 Sep 1984
- Country of Publication:
- United States
- Language:
- English
Similar Records
Microenvironment effects on the kinetics of electron-transfer reactions involving dithionite ions and viologens. 1. A comparison between two types of polyelectrolytes
Effect of iridium(IV) oxides on the decay of zinc tetrakis(N-methylpyridinium-4-yl)porphyrin. pi. -radical cation in the presence of poly(styrenesulfonate)
Related Subjects
400500* -- Photochemistry
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COMPLEXES
ELECTROLYTES
ELECTRON TRANSFER
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYMERS
PORPHYRINS
SOLID ELECTROLYTES
ZINC COMPLEXES