Title

聯?啶?錯合物的性質研究

Translated Titles

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

Authors

陳喧應

Key Words

; 釕 ; bipyridine ; Ruthenium

PublicationName

臺灣師範大學化學系學位論文

Volume or Term/Year and Month of Publication

2000年

Academic Degree Category

碩士

Advisor

張一知

Content Language

繁體中文

English Abstract

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.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系
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