聯?啶?錯合物的性質研究

The study of Ruthenium(II) tris(dipyridyl) complexes

陳喧應(Hsuan Ying Chen)

指導教授 ： 張一知

國立臺灣師範大學/理學院/化學系/碩士(2000年)

摘要

無資料

關鍵字

釕

並列摘要

Abstract
Ruthenium(II) tris(dipyridyl) complexes have been synthesized. By varying the electron-withdrawing and electron-donating abilities on each bipyridyl ligand, we have made eight complexes that contain at least one 4-carboxyl-4’-methy,2’-bipyridine or 4-carboxyl-3,3’4,’-trimethy,2’-bipyridine. These complexes are Ru(phen)2(mcbpy)2+, Ru(tmbpy)2(mcbpy) 2+, Ru(dmbpy)2(mcbpy) 2+, Ru(bpy)2(mcbpy) 2+, Ru(dnbpy)2(mcbpy) 2+, Ru(bpy)2(tmcbpy) 2+, Ru(dcbpy)2(mcbpy) 2+, Ru(dcbpy)2(tmcbpy) 2+.
The ground-state acid dissociation constant (pKa) were obtained from the titration curve of absorption changes. The excited-state acid dissociation constant (pKa*) were obtained from the luminescence titration curve and lifetime calibration. A positive ΔpKa (ΔpKa = pKa* - pKa) indicates the electron density of the bipyridine that contains the carboxyl group has a higher electron density in the excited state than the ground state. A negative ΔpKa indicates the carboxyl containing bipyridine has less electron density in the excited state . From the acid dissociation constant studies, the electron density in the excited state of Ruthenium(II) tris(dipyridyl) complexes can be qualitatively mapped.
The experiment data forΔpKa are 0.95, 0.93, 0.71, 0.27, 0.02, -0.87, -3.55 and -3.57 for Ru(phen)2(mcbpy) 2+, Ru(tmbpy)2(mcbpy) 2+, Ru(dmbpy)2(mcbpy) 2+, Ru(bpy)2(mcbpy) 2+, Ru(dnbpy)2(mcbpy) 2+, Ru(dcbpy)2(mcbpy) 2+, Ru(bpy)2(tmcbpy) 2+ and Ru(dcbpy)2(tmcbpy) 2+, respectively. The results indicate that if it is desired to have higher electron density in the excited state on the carboxyl containing bipyridine, [Ru(phen)2(mcbpy)] is the best choise. On the other hand, if carboxyl containing bipyridine is designated to have less electron density in the excited state , [Ru(dcbpy)2(tmcbpy)] is the best candidate.

並列關鍵字

bipyridine ； Ruthenium

參考文獻

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