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|Type of Document
||1. Pronounced Effects of Grinding on Rates of Intramolecular Electron Transfer in Tetranaphthylmethyl Substituted Mixed- Valence Biferrocenium Triiodide.|
2. The Application of Terpyridinyl Substituted Biferrocene Complexes in the Development of Molecular Wires: Preparations and Characterization.
|Date of Defense
The X-ray structural determinations of the neutral 1',2',1'",2'"-tetranaphthylmethyl- and the 1', 3', 1', 3'-tetranaphthylmethyl- biferrocenium triiodide have been determined. Our Mossbauer measurement for 1.34 and 1.35 indicate that the intramolecular electron transfer rates are quite sensitive to the environmental perturbations caused by the grinding of the sample. An interesting finding is that the Mossbauer results indicate that the unground diffusing sample of 1.34 is valence delocalized on the Mossbauer time scale above 180K. However, the ground diffusing sample of 1.34 exhibits a Mossbauer spectrum characteristic of a valence-trapped cation which remains valence-trapped electronic state at 300K. The effects of grinding of samples are also observed in the EPR and XRD measurements.
A great deal of research has concentrated on long range electron and energy transport in transition metal- based system and conducting polymer. We have synthesis a new bis-terpyridine bridging ligand (2.40) which the spacer is biferrocene moiety. Incorporating of the Ruthenium (II) subunits via redox-active spacer group promote to construction polynuclear transition metal complexes (i.e. multicomponent system). Cyclic voltammetric analysis indicated that there are Fe-Fe electronic coupling in the bridging ligand, and the degree of Fe-Ru electronic coupling is weak. In addition to dominant UV absorption near 240 and 280 nm from terpyridinyl and MLCT absorption from Ru to terpyridine around 480 nm, the complexes containing ferrocene or biferrocene as endgroup exhibit an unusual absorption band around 560 nm which is due to a feccocene moiety to terpyridine MLCT transition.
||Chin-Hsing Chou - chair|
Nein-Chen Chang - co-chair
Lan-Chang Liang - co-chair
Wen-Yann Yeh - co-chair
Teng-Yuan Dong - advisor
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