| Polypyridine complexes containing transition metal ions such as Ru, Os, and Re possess a remarkable wealth of photochemical and electrochemical properties. This combination makes them versatile candidates for unique photonic and electronic applications. The first chapter details the use of two metal polypyridine complexes in the development of a two-step novel fabrication technique which combines photostatically and electropolymerization (PL-EP). This technique allows for the production of microstructured polymer-modified electrodes whose films may act as gratings which possess interesting electrochemical and optical properties. In the photolithographic step, a solution of poly-methylphenylsilane (p-MPS) is applied to an electrode surface and used as a photoresist, creating a patterned framework of p-MPS on the electrode. The second step in the method is the electropolymerization of a monomer solution of either ((bpy){dollar}sb2{dollar}Ru(vpy){dollar}sb2rbracksp{lcub}2+{rcub}{dollar} or (Os(vbpy){dollar}sb3rbracksp{lcub}2+{rcub}{dollar} where bpy = 2,2{dollar}spprime{dollar}-bipyridine, vpy = 4-vinylpyridine, and vbpy = 4, methyl-4{dollar}spprime{dollar}-vinyl-2,2{dollar}spprime{dollar}-bipyridine. The polymer is grown on the electrode areas which are not covered by the patterned p-MPS. A final development step results in microstructured arrays of electroactive polymers with high spatial resolution on the order of 5 {dollar}mu{dollar}m. Because of the periodicity of the polymer arrays, these films act as gratings, and diffract light. The interesting feature of these grating films is that the amount of light diffracted, the diffraction efficiency, DE can be modulated by controlling the electrochemical potential applied to the electroactive polymer electrode, i.e., oxidation or reduction of the patterned film results in a decrease or increase in the film's diffraction efficiency, respectively. The origin of the observed dependency of the DE with the redox state of the film is attributed to a change in the film's refractive index upon applying an electrical potential. Grating films produced by the PGEP method show excellent stability to repetitive electrochemical cycling and fast charge transport, allowing for their DEs to be optically switched at 2 sec intervals.; The versatility of such polypyridine complexes is further detailed in the second chapter which focuses on their interesting luminescence properties rather than their electrochemical properties. The luminescence of metal polypyridine complexes is often temperature dependent, and careful manipulation of their chemical structure can yield complexes whose emission properties may allow for their use as temperature sensitive probes. The successful synthesis and design strategy of two novel heteroleptic polypyridyl Ru complexes, Rutdp and Rutpm, (where Rutdp = ruthenium(II)(2,2{dollar}spprime:6spprime,2sp{lcub}primeprime{rcub}{dollar}- terpyridine)(4,7-diphenyl-1,10-phenanthroline)(pyridine) hexafluorophosphate and Rutpm = ruthenium(II)(tris(1-pyrazolyl)methane)(4,7-diphenyl-1,10- phenanthroline)(pyridine) hexafluorophosphate) whose luminescence is temperature sensitive in the 100-298 K region is reported. The photophysics of these complexes is reported for room temperature solutions, low temperature glasses and for experiments where these complexes have been doped into a polymeric binder, allowing them to be painted on surfaces. |
