Charge Transfer in Multiple Site Chemical Systems.
Abstract
This report covers work done by the author in both mixed-valence dimers and metallopolymers. Concerning the dimers, crystal structures of related monomers were obtained to judge the adequacy of classical approximations in calculating inner-sphere vibrational trapping. A series of homometallic and heterometallic dimers were prepared and a relationship between redox asymmetry and intervalence transfer absorption band energy was found. Electronic structure was observed in the intervalence transfer absorption band of an OS(II)-Os(III) mixed-valence dimer, owing to the presence of well-separated spin orbit states in Os(III). Other dimers were prepared to study the transitions between various states within the dimers. Both metal to metal and ligand to ligand electron transfer was seen in optically prepared mixed-valence dimers. Concerning the polymers, redox-site incorporation into poly-vinylpyridine, P-chlorosulfonated polystyrene and oxidatively electro-polymerized films were studied. Characterization and stability of these films as well as comparison to monomeric analogues was accomplished. Practical application of the metallopolymers include their use as a chromophore in a photoelectrochemical cell and as a catalyst for the oxidation of C1- to C12.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 30, 1985
- Accession Number
- ADA157413
Entities
People
- T. J. Meyer
Organizations
- University of North Carolina at Chapel Hill