聯?啶?錯合物與??化合物之性質與應用

鍾昭國(Chung Chao Kuo)

指導教授 ： 張一知

國立臺灣師範大學/理學院/化學系/碩士(2003年)

並列摘要

Three Ruthenium trisbipyridine complexes have been synthesized. Two of the bipyridine ligands have been substituted by two polymethylene chain with terminal carboxyl acid groups ((CH2)nCOOH：n = 7, 12, and 17) at the 4-4’ position of the bipyridine.
These complexes have been covalently bound to TiO2 nanoparticles via carboxylate group. Femtosecond laser spectroscopy were used to investigate the photoinduced electron-transfer reaction between the Ruthenium complexes and the TiO2 nanopartilces.
The electron-transfer rates are 3.85×1012、4.17×1012、4.76×1012 s-1 for [Ru(d7cbpy)2(bpy)]2+、[Ru(d12cbpy)2(bpy)]2+、[Ru(d17cbpy)2(bpy)]2+; respectively. The lifetime of physically absorbed [Ru(bpy3)]2+ on TiO2 surface is 0.26 ps. These sub-picosecond rates are similar in all four complexes indicating a similar electron transfer pathway. Compare to the electron transfer rates in solution at comparable distance, the rates are too fast to transfer through bonds. We conclude that the electron transfer to the nearest TiO2 nanoparticle, either through bond or by physical contact.
The TiO2 nanorods has been made successfully by useing anodic aluminum oxide membrane as template. The length of the rods are within 500~1000 nm, and the diameter of the rods are in the range of 160~260 nm.
A methyl viologen based electron acceptor substituted with rich electron-withdrawing groups, Cl6O2MV2+, were synthesis. The redox potential of Cl6O2MV2+ is -0.06 V, the bimolecular quench rate constant, kq, of the compound and [Ru(bpy3)]2+ is 1.63×108 M-1s-1.
The photochemistry of N-confused porphyrin in the CHCl3 can be understood through various studies, such as irradiating methods, kinetic isotope effect, and the GC/EI-Mass. The pKa of N-confused porphyrin can be measured by UV-Vis spectrum to be 8.11~8.33.

並列關鍵字

Ru(bpy)3, TiO2

參考文獻

3) Winkler, J. R.; Gray, H. B. Chem. Rev. 1992, 92, 369.

4) Tsai, T.-C.; Chang, I.-J. J. Am. Chem. Soc. 1998, 120, 227.

6) Rutherford, T. J.; Keene, F. R. Inorg. Chem. 1997, 36, 2872.

8) Honda, K.; Fujishima, A. Nature 1972, 238, 37.

9) Tufts, B. J. Nature 1987, 326, 681.