Accession Number : ADA157413


Title :   Charge Transfer in Multiple Site Chemical Systems.


Descriptive Note : Final rept. Apr 82-Apr 85,


Corporate Author : NORTH CAROLINA UNIV AT CHAPEL HILL DEPT OF CHEMISTRY


Personal Author(s) : Meyer,T J


Full Text : http://www.dtic.mil/dtic/tr/fulltext/u2/a157413.pdf


Report Date : 30 May 1985


Pagination or Media Count : 18


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.


Descriptors :   *METALS , *POLYMERS , *ELECTRON TRANSFER , *DIMERS , POLYSTYRENE , TRAPPING(CHARGED PARTICLES) , ELECTRODES , LIGANDS , POLYMERIC FILMS , BAND SPECTRA , PYRIDINES , OXIDATION REDUCTION REACTIONS , VINYL PLASTICS , OSMIUM , PHOTOELECTRIC CELLS(SEMICONDUCTOR)


Subject Categories : Polymer Chemistry
      Atomic and Molecular Physics and Spectroscopy


Distribution Statement : APPROVED FOR PUBLIC RELEASE