Accession Number : ADA288719

Title :   Toward Molecular Selectivity with Chemically Modified Electrodes: Can Electroactivity and Permeability through an Overlaying Metallopolymer Film be Controlled via Rational Manipulation of Internal Architecture?.

Descriptive Note : Technical rept.,

Corporate Author : NORTHWESTERN UNIV EVANSTON IL DEPT OF CHEMISTRY

Personal Author(s) : Yan, Susan G. ; Hupp, Joseph T.

PDF Url : ADA288719

Report Date : 30 NOV 1994

Pagination or Media Count : 26

Abstract : Metallopolymeric films featuring widely varying metal-to-metal linkage lengths have been prepared via a combination of oxidative and reductive electropolymerization schemes. Each of the film materials exhibits strong size selective permeability behavior towards molecular reactants - providing a primitive physical basis, therefore, for selectivity with respect to reactivity at an underlying electrode. Surprisingly, the observed molecular size cutoffs are essentially independent of film composition, implying that a uniform molecular cavity or pore size exists. Attempts to modify effective pore sizes by introducing large ligand substituents (phenyl groups) at the monomer synthesis stage have failed to alter the pattern of size selectivity. We speculate that: (a) potential pore size expansion effects expected from linkage length extension are offset by enhanced cross linking, and/or (b) electrolyte anion templating effects during film synthesis may be defining the effective minimum pore size, thereby yielding uniform permeation size cutoffs.

Descriptors :   *MODIFICATION, *ELECTRODES, *MOLECULAR PROPERTIES, METALS, PERMEABILITY, SIZES(DIMENSIONS), SYNTHESIS, MOLECULES, COMPOSITE MATERIALS, FILMS, REACTIVITIES, ELECTROCHEMISTRY, CAVITIES, CROSSLINKING(CHEMISTRY), INTERNAL, LENGTH, LIGANDS, PATTERNS, MONOMERS, ELECTROLYTES, ARCHITECTURE, LINKAGES, ANIONS, PHENOLS, REACTANTS(CHEMISTRY).

Subject Categories : Electrical and Electronic Equipment
      Physical Chemistry
      Polymer Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE