Competitive isomerization and dimerization in co-crystals of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol and sorbic acid: a new look at stereochemical requirements for [2+2] dimerization

Literature Information

Publication Date 2008-03-31
DOI 10.1039/B802103A
Impact Factor 6.222
Authors

Shao-Liang Zheng, Oanh Pham, Christophe M. L. Vande Velde, Milan Gembicky, Philip Coppens


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Abstract

Competitive [2+2] photodimerization and E→Z isomerization reactions occur in a co-crystal of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol upon irradiation with 325 nm light. At 90 K both reactions are observed, whereas at 280 K the dimerization reaction is very fast and inhibits isomerization as the nature of the chromophore is affected by the reaction. The temperature dependence of the stereospecificity of the dimerization reaction is related to the large sliding motion required to bring the reacting molecules into juxtaposition. The progress of the reactions has been monitored by photocrystallographic methods.

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