Photoinduced electron transfer, catalysis complexation

A biomimetic artificial photylase model was described by Wiest et al. [18] The model recognised pyrimidine dimers in both organic solvents and water. Excitation of the complex with visible light led to cycloreversion of the pyrimidine dimer through photoinduced electron-transfer catalysis (Scheme 21). 

If a third component (M), which can specifically stabilize one of the products of electron transfer, is introduced into the D -A system, the free energy change of photoinduced electron transfer is shifted to the negative direction, when the activation barrier of electron transfer is reduced to accelerate the rates of electron transfer, as shown in Figure 3, where M forms a complex with A ". It should be emphasized that there is no need to have an interaction of M with A and that the interaction with the reduced state (A ") is sufficient to accelerate the rate of photoinduced electron transfer. This contrasts sharply with the catalysis on conventional ionic or concerted reactions, in which the catalyst interacts with a reactant to accelerate the reactions. The initial interaction between M and A in the complex A-M, where charge is partially transferred from A to M, would also result in acceleration of the photoinduced electron transfer, since the reduction potential of A-M is shifted to the negative direction as compared to that of A. 

The catalytic effect of metal ions such as Mg2+ and Zn2+ on the reduction of carbonyl compounds has extensively been studied in connection with the involvement of metal ions in the oxidation-reduction reactions of nicotinamide coenzymes [144-149]. Acceleration effects of Mg2+ on hydride transfer from NADH model compounds to carbonyl compounds have been shown to be ascribed to the catalysis on the initial electron transfer process, which is the rate-determining step of the overall hydride transfer reactions [16,87,149]. The Mg2+ ion has also been shown to accelerate electron transfer from cis-dialkylcobalt(III) complexes to p-ben-zoquinone derivatives [150,151]. In this context, a remarkable catalytic effect of Mg2+ was also found on photoinduced electron transfer reactions from various electron donors to flavin analogs in 1984 [152], The Mg2+ (or Zn2+) ion forms complexes with a flavin analog la and 5-deazaflavins 2a-c with a 1 1 stoichiometry in dry MeCN at 298 K [153] ... 

As demonstrated in this review, photoinduced electron transfer reactions are accelerated by appropriate third components acting as catalysts when the products of electron transfer form complexes with the catalysts. Such catalysis on electron transfer processes is particularly important to control the redox reactions in which the photoinduced electron transfer processes are involved as the rate-determining steps followed by facile follow-up steps involving cleavage and formation of chemical bonds. Once the thermodynamic properties of the complexation of adds and metal ions are obtained, we can predict the kinetic formulation on the catalytic activity. We have recently found that various metal ions, in particular rare-earth metal ions, act as very effident catalysts in electron transfer reactions of carbonyl compounds [216]. When one thinks about only two-electron reduction of a substrate (A), the reduction and protonation give 9 spedes at different oxidation and protonation states, as shown in Scheme 29. Each species can... 

When over-stoechiometric amounts of ligands are used, it has been known since long that tris bipyridyl complexes [41, 42] are formed which are not active in dark catalysis but show interesting properties as photocatalyst [43]. Photoinduced electron transfer from encaged [Ru(BPY)3]NaX to methylviologen is 2 orders more... 

The energetic process of photosynthesis is represented by Fig. 13-1 where the electron from water is driven to higher energy in two steps (at photosystems II and I, abbreviated to PSII and I) at the reaction center of chlorophyll, and finally reduces CO2 to produce carbohydrate. Metal complexes and metal clusters play a decisive role in photoinduced energy transfer, photoinduced electron transfer and catalysis. 

The interest in highly branched polynuclear metal complexes, and more generally in dendritic species, is related not so much to their size, but rather to the presence of different components. An ordered array of different components can in fact generate valuable properties, such as the presence of cavities having different size, surfaces with specific functions, gradients for photoinduced directional energy and electron transfer, and sites for multielectron transfer catalysis. Studies along these directions are underway in our laboratories. 

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