Study of Intermediates from Transition Metal Excited-state Electron-transfer Reactions. [Annual] Progress Report, August 1, 1989--July 31, 1992 PDF Download
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Languages : en
Pages : 19
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Conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used to study the intermediates involved in transition metal excited-state electron-transfer reactions. These intermediates were excited state of Ru(II) and Cr(III) photosensitizers, their reduced forms, and species formed in reactions of redox quenchers and electron-transfer agents. Of particular concern was the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes. (DLC).
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Languages : en
Pages : 19
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Conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used to study the intermediates involved in transition metal excited-state electron-transfer reactions. These intermediates were excited state of Ru(II) and Cr(III) photosensitizers, their reduced forms, and species formed in reactions of redox quenchers and electron-transfer agents. Of particular concern was the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes. (DLC).
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Category : Power resources
Languages : en
Pages : 654
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Author:
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ISBN:
Category :
Languages : en
Pages : 19
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Book Description
During this period, conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used for the characterization of the intermediates that are involved in transition metal excited-state electron-transfer reactions. The intermediates of interest were the excited states of Ru(II) and Cr(III) photosensitizers, their reduced forms, and the species formed in the reactions of redox quenchers and electron-transfer agents. Of particular concern has been the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes.
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Languages : en
Pages : 5
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Progress on 6 projects is reported: excited state absorption spectrum of Ru(bpy)3{sup 2+}, solvent cage model for electron transfer quenching, reductive quenching of {sup *}Cr(III) complexes, solution medium effects in oxidative quenching of {sup *}Ru(II) complexes, photosensitized oxidation of phenol in aqueous solution, and quenching of Ru(II) complexes by oxygen.
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Category : Research
Languages : en
Pages : 1190
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Sections 1-2. Keyword Index.--Section 3. Personal author index.--Section 4. Corporate author index.-- Section 5. Contract/grant number index, NTIS order/report number index 1-E.--Section 6. NTIS order/report number index F-Z.
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Languages : en
Pages : 31
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The techniques of continuous photolysis and pulsed laser flash photolysis, continuous and pulse radiolysis, fast-scan cyclic voltammetry, and time-resolved fluorimetry have been used to examine intramolecular electron transfer within the solvent quenching cage, photodynamics of quenching of the excited states of transition-metal photosensitizers, the properties of excites states and one-electron reduced forms, ground- and excited-state interactions with solutes, and photoinduced oxidations of organic solutes in aqueous solution. The following specific areas were examined: (1) the parameters that govern the yields of redox products from excited-state electron-transfer quenching reactions; (2) the mediation of the properties of excited states and one-electron reduced forms by the ligands and the solution medium; (3) the effect of the interactions between the ground state of the complex and the solution components on the behavior of the excited state; (4) the yields of singlet oxygen from excited-state energy-transfer quenching by O2; and (5) the oxidations of solutes by singlet oxygen, excited-state electron-transfer quenching, and free radicals. This report contains the abstracts of 50 publications describing the studies.
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Languages : en
Pages : 5
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Progress on 6 projects is reported: excited state absorption spectrum of Ru(bpy)[sub 3][sup 2+], solvent cage model for electron transfer quenching, reductive quenching of [sup *]Cr(III) complexes, solution medium effects in oxidative quenching of [sup *]Ru(II) complexes, photosensitized oxidation of phenol in aqueous solution, and quenching of Ru(II) complexes by oxygen.
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Category : Science
Languages : en
Pages : 1306
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Category :
Languages : en
Pages : 9
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In our research there were two major themes. The first was the continued development of excited states as sensitizers. In one sequence of experiments the synthetic aspects of this area were developed in further detail both by extending the chemistry of the polypyridyl-accepting ligands associated with the excited state and by developing a new procedure for the preparation of unsymmetrical tris-chelate complexes. The second important aspect of this work was the continued investigation of the molecular and electronic structure characteristics of this class of excited states and how those factors determine such properties as photostability and excited state decay. This effort was extended to complexes of Re(I) and an examination of their excited state characteristics, the role of hydride ligand in determining the properties of excited states, the calculation of relative nonradiative decay rate constants for a series of complexes of Ru(II), the participation of higher lying excited states in decay in complexes of Ru(II) and Os(II), and the application of the transient infrared technique to the elucidation of a photochemical intermediate following laser flash excitation. The second area of study involved excited states in soluble polymers to investigate photoinduced electron and energy transfer in multi-component assemblies. This work was based on chemically derivatized polystyrene polymers which contain combinations of chromophores and electron or energy transfer quenchers.
Author: Russell Hunter Schmehl
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Category : Charge transfer
Languages : en
Pages : 446
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