Polyelectrolytes as interfaces for retarding back-reaction in photoinduced electron transfer

Conference · Wed Aug 01 00:00:00 EDT 1984

OSTI ID:6454504

Otvos, J W; Casti, T E; Calvin, M

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 National Laboratory (LBNL), Berkeley, CA (United States)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6454504
• Report Number(s): LBL-18290; CONF-8409141-1; ON: DE85000713
• Resource Relation: Conference: Photochemistry of metal complexes conference, Tokyo, Japan, 2 Sep 1984
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PORPHYRINS
PHOTOCHEMICAL REACTIONS
SOLID ELECTROLYTES
POLYMERS
ZINC COMPLEXES
CATALYTIC EFFECTS
ELECTRON TRANSFER
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COMPLEXES
ELECTROLYTES
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
400500* - Photochemistry