Electron transfer reactions, photoinduced

Sekiguchi S, Kobori Y, Akiyama K and Tero-Kubota S 1998 Marcus free energy dependence of the sign of exchange interactions in radical ion pairs generated by photoinduced electron transfer reactions J. Am. Chem. Soc. 120 1325-6... 

A review of the role of thiols as electron donors in photoinduced electron-transfer reactions has been compiled (49). 

Photoinduced electron transfer reactions in supramolecularmodel systems based on metalloporphyrins 97YGK557. 

Since the electrostatic potential sharply decreases with increasing distance from the polyelectrolyte cylinder, the degree of reactivity modification by functional groups fixed to the polyion is strongly dependent on the distance from the cylinder surface. Considerable electrostatic potential effects on the photoinduced forward and thermal back electron transfer reactions, which will be discussed in the following chapters, can be attributed to the functional chromophore groups directly attached to the polyelectrolyte back-bone through covalent bonds. 

Photoinduced electron-transfer reactions of metal complexes in solution. D. G. Whitten, Acc. Chem. Res., 1980,13, 83-90 (105). 

Photoinduced Electron Transfer Reactions of Gold Complexes 273... 

Recently, photochemical and photoelectrochemical properties of fullerene (Cto) have been widely studied [60]. Photoinduced electron-transfer reactions of donor-Qo linked molecules have also been reported [61-63]. In a series of donor-Cfio linked systems, some of the compounds show novel properties, which accelerate photoinduced charge separation and decelerate charge recombination [61, 62]. These properties have been explained by the remarkably small reorganization energy in their electron-transfer reactions. The porphyrin-Qo linked compounds, where the porphyrin moieties act as both donors and sensitizers, have been extensively studied [61, 62]. 

It has been reported that Cgo and its derivatives form optically transparent microscopic clusters in mixed solvents [25, 26]. Photoinduced electron-transfer and photoelectrochemical reactions using the C o clusters have been extensively reported because of the interesting properties of C o clusters [25,26]. The M F Es on the decay of the radical pair between a Cgo cluster anion and a pyrene cation have been observed in a micellar system [63]. However, the MFEs on the photoinduced electron-transfer reactions using the Cgo cluster in mixed solvents have not yet been studied. 

Yonemura, H., Noda, M., Hayashi, K, Tokudome, H., Moribe, S. andYamada, S. (2002) Photoinduced intramolecular electron transfer reactions in fiillerene-phenothiazine linked compounds effects of magnetic field and spacer chain length. Mol. Phys., 100, 1395-1403. 

In good electron acceptor solvents, such as carbon tetrachloride and chloroform, the photodegradation of carotenoids is significantly increased as compared to other solvents (Christophersen et al. 1991, Mortensen and Skibsted 1999), because of a direct photoinduced electron-transfer reaction from the excited singlet state of the carotenoids to the solvent, as determined by transient absorption spectroscopy (Jeevarajan et al. 1996, Mortensen and Skibsted 1996,1997a,b, El-Agamey et al. 2005), Equation 12.2 ... 

Scheme 5.1. Stereoselective domino cyclization via photoinduced electron-transfer reaction.

Chow TJ, Chiu NR, Chen HC et al (2003) Photoinduced electron transfer reaction tuned by donor-acceptor pairs via rigid linear spacer heptacyclo[6.6.0.02, 6.03, 13.04, 11.05, 9.010, 14]tetradecane. Tetrahedron 59 5719-5730... 

Other radical cyclization approaches to the synthesis of piperidines include a CAN-mediated stereoselective cyclization of epoxypropyl cinnamyl amines <06TL705> and a cyclization of (-trimethylsilylmethylamine radical cation, generated via a photoinduced electron transfer reaction to a tethered -functionality <06JOC8481>. 

C. Shen and N.M. Kostic. Kinetics of photoinduced electron-transfer reactions within sol-gel silica glass doped with zinc cytochrome c. Study of electrostatic effects in confined liquids. J. Am. Chem. Soc. 119, 1304-1312 (1997). 

In a number of cases ITIES can be used to separate the products of a photoinduced electron-transfer reaction. An early example is the work by Willner et al. [7] at the water/toluene interface, who studied the photooxidation of [Ru(bpy)3]2+ in the aqueous phase. The excited state was quenched by hexadecyl- 4,4 bipyridinium, which becomes hydrophobic on reduction and crosses to the toluene phase. There are other examples and mechanisms at the present time their main interest resides in their chemistry, and in the separation of products that can be achieved at the interface. 

Photoinduced electron transfer reactions between surface bound dye molecules and semiconductor electrodes are important for practical as well as fundamental reasons. Absorption of light by the dye can improve the spectral response of the semiconductor and these systems are models for the photographic process (47-511. MDC surfaces are excellent substrates for studying electron injection into the conduction band of the semiconductor. 

Y. Zeng, M. B. Zimmt, Symmetiy Effects in Photoinduced Electron Transfer Reactions , J. Am. Chem. Soc 1991,113,5107-5109. 

Sabbatini N, Dellonte S, Bonazzi A et al (1986) Photoinduced electron-transfer reactions of poly(pyridine)ruthenium(II) complexes with europium(III/II) cryptates. Inorg Chem 25 1738-1742... 

The importance of tertiary amines in the photochemically induced electron transfer reactions has also been addressed5. Direct irradiation of aromatic or aliphatic amines often leads to the scission of C—N, N—H or C—H bonds that lead to the subsequent chemical reactions by radical pathways6. In this section, photochemical reactions of amines reported since 1978 will be considered with emphasis on photoinduced electron transfer. Photochemical reactions of inorganic and organometallic compounds will not be included unless photochemistry of amine moieties is the primary interest. 

The chapters in this Supplement F2 generally contain references up to the middle of 1995. Of the planned contents of this book, only three chapters failed to materialize. These were on NQR and ESR, on pyrolysis, and on photoinduced electron transfer reactions. I hope that these missing subjects will be dealt with in a later forthcoming supplementary volume of the series. 

Scheme 6.—Proposed Mechanism for the Photoinduced, Electron-transfer Reaction of Phenyl /3-D-Glucypyranoside with 1,4-Dicyanonaphthalene (DCN) in 1 10 Methanol-Acetonitrile. Irradiation at 350 nm was Continued for 72 h.

Designing a conjugated polymer sensor based on FQ, however, is not only a matter of making a fluorescent polymer for which the photoinduced electron transfer reaction is energetically favorable. There are other important factors that must be considered and requirements that must be met to rehably detect any analyte of interest, including TNT, from the vapor phase. In the broadest sense, these considerations distill to the two primary considerations for any sensing system, sensitivity and selectivity. 

Until now, the isotopic effect was discnssed only in relation to the reactants. In electron-transfer reactions, the solvent plays an eqnally important role. As mentioned, different solvate forms are possible for reactants, transition states, and products. Therefore, it seems important to find a reaction where the kinetic effect resulting from the introduction of an isotope would be present for solvents, but absent for reactants. For a published work concerning this problem, refer Yusupov and Hairutdinov (1987). In this work, the authors studied photoinduced electron transfer from magnesium ethioporphyrin to chloroform followed by a dark recombination of ion-radicals in frozen alcohol solutions. It was determined that the deuteration of chloroform does not affect the rate of transfer, whereas deuteration of the solvent reduces it. The authors correlate these results with the participation of solvent vibrational modes in the manner of energy diffraction during electron transfer. 

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