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Abstract: Mechanistic studies and product analyses were performed on the single electron transfer (SET) promoted photoamination reaction between 2,5-dimethylhexa-2,4-diene (1) and 9-cyanophenanthrene in order to gain a comprehensive understanding of the effects of additive metal salts. The product selectivity of this process was found to be dramatically increased by the addition of Mg2+ salts. An investigation involving the analyses of fluorescence and time-resolved absorption spectroscopic properties reveals that Mg2+ enhances the rate of the initial SET step and stabilizes the resulting radical ion pair in this photoreaction. [Copyright &y& Elsevier]

Photochemical reactions of 2,5-bis[2,2-di(thien-2-yl)ethenyl]thiophene ( 1a ) and its tetramethyl derivative 1b , under direct photoexcitation, and photoinduced electron-transfer conditions, were studied. Our initial prediction was that 1b would undergo a photoreaction as part of a reversible photochromic system, while a reaction of its non-methyl substituted analog 1a would undergo a typical double sequence of 6π-electrocyclization (6π-EC)/aromatization (AR) (double dehydrogenation, 2H) to give 7,11-di(thien-2-yl)trithia[5]helicene ( 2a ). In fact, we observed that photoirradiation of 1b leads to formation of the 7,11-bis(3-methylthien-2-yl)trithia[5]helicene ( 2b ). In this process, 2b is formed via a double sequence of 6π-EC/AR (dehydrogenation/demethylation, H/ Me). Moreover, the yield of formation of 2b is much higher than that of 2a , which reacts through a double sequence of 6π-EC/AR ( 2H). Thus, this photochemically-induced paradoxical cascade reaction based on the newly uncovered reactivity serves as an efficient method to construct the trithia[5]helicene framework. [ABSTRACT FROM AUTHOR]