Excited state processes in transition metal complexes. Redox splitting in soluble polymers. Progress report, July 15, 1993--July 14, 1994

摘要

In the past grant period, this DOE supported work has progressed considerably in the rational design of polypyridyl complexes of ruthenium(II), osmium(II), and rhenium(I) that exhibit predetermined photochemical, photophysical, and redox properties. The exploration of molecular design has moved forward along four fronts. The author's have developed a synthetic strategy for the preparation of heteroleptic complexes based on ruthenium(II) that contain three different bidentate ligands. Second, the authors are utilizing this synthetic procedure to prepare complexes with broad band absorbance throughout the UV and visible regions of the spectrum, so called (open quotes)black absorbers.(close quotes) Third, the authors have utilized more traditional synthetic procedures to prepare an extended series of nitro and nitrosyl containing complexes that could provide the basis for emission-based pH determination. Fourth, the controlled immobilization of the d(sup 6) chromophores on soluble styrenic polymers is under investigation in an attempt to study long range electron and energy transfer. Additionally, the authors have established protocols for the elucidation of excited state dynamics by utilizing time-resolved resonance Raman and transient infrared spectroscopies, as well as emission spectral fitting techniques. These studies have lead to the publication or submission of nine manuscripts during the budget period.