Ferrocenylenegermane Polymers and Copolymers

Abstract

Ferrocenylenegermane polymers and copolymers (1) have been prepared, in situ, by thermal treatment of the product from the reaction between dilithioferrocene and the corresponding R2GeCl2, R = methyl (1a), ethyl (1b), n-butyl (1c), or their mixtures, Me2GeCl2+ n-Bu2-GeCl2(1d) and Et2GeCl2+ n-Bu2GeCl2 (1e). Thin films of the polymers can exhibit both semicrystalline or amorphous morphology dependent upon the nature of the alkyl group and/or mode of casting. When cast from THF, 1c was observed as an amorphous material; however, after time a crystalline form was obtained. Films of mixed polymer systems, 1b + 1c, cast from THF immediately resulted in crystalline forms for both polymers, i.e., a seeding of 1c by 1b occurred. The diethyl/di-n-butyl copolymer was amorphous and elastomeric as was the dimethyl/di-n-butyl analog. Cyclic voltammetry indicated the presence of two reversible redox couples in solution with potentials slightly higher than the Si analogs. The copolymers also exhibited distinctive electrochemistry and not a combination of the two individual components. © 1995, American Chemical Society. All rights reserved.