Photochemistry photo-electron transfer

Numerous such reactions can be found in the exhaustive book of Balzani and Carassiti on the photochemistry of coordination compounds, published in 1970 [1]. This monograph was of extreme importance in the development of this research area. It is noteworthy that it contains relatively little photo-redox chemistry it is only about ten years ago that electron transfer in the excited state was considered to be important. Interestingly, a special issue of the Journal of Chemical Education was recently devoted to inorganic photochemistry [2] electron transfer reactions are clearly among the most studied and applied photochemical reactions of today. 

The low solubility of fullerene (Ceo) in common organic solvents such as THE, MeCN and DCM interferes with its functionalization, which is a key step for its synthetic applications. Solid state photochemistry is a powerful strategy for overcoming this difficulty. Thus a 1 1 mixture of Cgo and 9-methylanthra-cene (Equation 4.10, R = Me) exposed to a high-pressure mercury lamp gives the adduct 72 (R = Me) with 68% conversion [51]. No 9-methylanthracene dimers were detected. Anthracene does not react with Ceo under these conditions this has been correlated to its ionization potential which is lower than that of the 9-methyl derivative. This suggests that the Diels-Alder reaction proceeds via photo-induced electron transfer from 9-methylanthracene to the triplet excited state of Ceo-... 

There is always interest in the photochemistry of the pyrimidine nucleic acid bases and related simple pyrimidinones, due to its importance in genetic mutation. In addition to damaging DNA, photo-induced reactions may also repair the damage, as in the reduction, by FADH, of the thymine glycol 64 back to thymine <06JACS10934>. Another report related to repair of DNA involved a model study, by means of the linked dimer 65, of the involvement of tryptophan in the electron-transfer leading to reversion of thymine oxetane adducts <06OBC291>. 

Topics which have formed the subjects of reviews this year include organic photo-oxidation reactions, synthetic aspects of organic photochemistry in the presence of oxygen, electron transfer reactions involving oxygen, and the photo-oxidation of mercaptopteridines/... 

Yehuda Haas was horn in Israel in 1939, In 1971 he received his Ph.D. from the Hebrew Llniversity of Jerusalem and has been on the staff of the Physical Chemistry Department since 1975, becoming a Professor in 1984. Between 1989 and 1992 he was Vice President for Research and Development of the University. Professor Haas has held several visiting positions at the Max-Pi anck-lnstitute in Gottingen (1980), at the University of Southern California in Los Angeles (1981), at the Uni-versite de Paris Sud in Orsay (1986), at the Institute of Molecular Science in Okazaki (1992), and at the University of Oxford (1996). His main scientific interests arc photochemistry and photophysics, laser-induced chemistry, photo-induced electron transfer, and matrix isolation. His publication list includes more than 120 papers and one book. 

Topics that have formed the subjects of reviews this year include contemporary issues in electron transport research, dynamics of bimolecular photoelectron transfer reactions, photophysical properties of functionalised fullerene derivatives, carbon-carbon bond formation via radical ions, photoinduced electron transfer processes in ketone, aldehyde, and ester synthesis, photochemical reactions between arenenitriles and benzylic donors, photo-oxidation of conjugated dienes, photoredox reactions of aromatic nitro compounds, electron transfer-mediated photochemistry of some unsaturated nitrogen-containing compounds, reactions of 02( Ag), carbon dioxide activation by aza-macrocyclic complexes, and photochromism of chalcone derivatives. ... 

There are totally 11 chromophores in the bacterial photosynthetic reaction center (PSRC) of Rhodopseudomonas (Rps.) virids. Since the excitation process of the reaction center is the primary event of the photo-induced electron transfer in the reaction center, the detailed analysis of the absorption spectrum is one of the key steps for the understanding of photochemistry of the system. The chromophores included in the PSRC are bacteriochlorophyll b dimer (special pair, P), bacteriochlorophyll in L- and M-branches (Bl and B ), bacteriopheophytin in L- and M-branches (Hl and Hm), menaquinone (MQ), ubiquinone (UQ) and four different hemes, c-552, c-554, c-556, and c-559 in c-type cytochrome subunit. 

The radical cation of (163) can be formed by electron transfer photochemistry and in methanol addition products are formed. A study of the photochemical reactivity of some novel 3-phenylnorbomadienes has been reported. Bichromo-phoric norbomadiene derivatives have also been synthesized and studied photo-chemically. A study of the photoisomerization of some norbomadienes has been carried out within the constrained environment of P-cyclodextrin. The bichromophoric system (164) undergoes intramolecular electron transfer by a through-bond mechanism on irradiation. The transfer is from the benzidine... 

Topics which have formed the subjects of reviews this year include excited state chemistry within zeolites, photoredox reactions in organic synthesis, selectivity control in one-electron reduction, the photochemistry of fullerenes, photochemical P-450 oxygenation of cyclohexene with water sensitized by dihydroxy-coordinated (tetraphenylporphyrinato)antimony(V) hexafluorophosphate, bio-mimetic radical polycyclisations of isoprenoid polyalkenes initiated by photo-induced electron transfer, photoinduced electron transfer involving C o/CjoJ comparisons between the photoinduced electron transfer reactions of 50 and aromatic carbonyl compounds, recent advances in the chemistry of pyrrolidino-fullerenes, ° photoinduced electron transfer in donor-linked fullerenes," supra-molecular model systems,and within dendrimer architecture,photoinduced electron transfer reactions of homoquinones, amines, and azo compounds, photoinduced reactions of five-membered monoheterocyclic compounds of the indigo group, photochemical and polymerisation reactions in solid Qo, photo- and redox-active [2]rotaxanes and [2]catenanes, ° reactions of sulfides and sulfenic acid derivatives with 02( Ag), photoprocesses of sulfoxides and related compounds, semiconductor photocatalysts,chemical fixation and photoreduction of carbon dioxide by metal phthalocyanines, and multiporphyrins as photosynthetic models. 

Several reviews have been published within the year which are of general relevance to the photoreactions of aromatic compounds. The subjects of these reviews include photochemistry in ionic liquids and in isotropic and anisotropic media, organic synthesis utilizing photoinduced electron-transfer reactions," heteroatom-directed photoarylation processes, photochromism, and photochemical molecular devices. Reviews more directly pertinent to the sections in the present chapter include those of the photoisomerization of five-membered heteroaromatic azoles, the photocycloaddition of benzene derivatives to alkenes, Diels-Alder additions of anthracenes, advances in the synthesis of polycyclic aromatic compounds, diarylethene-based photochromic switches, the photo-Fries rearrangement, and the application of Diels-Alder trapping of photogenerated o-xylenols to the synthesis of novel compounds. " A number of chapters in the two recently published handbooks of photochemistry and photobiology and in the revised edition of the text on photochromism are also pertinent to the current subject matter. 

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