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1 December 2002 The Low-temperature Photochemistry of s-cis Acyclic 1,3-Dienes
Michael Squillacote, Thomas Semple, JeWie Chen, Fengting Liang
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In this article we have examined the very low-temperature photochemistry of three acyclic 1,3-dienes. We have used high-temperature deposition techniques combined with matrix isolation to create samples enriched with the thermally meta-stable s-cis form. This technique has allowed us to examine the separate photochemistry of the s-cis and s-trans conformers. Our results suggest the presence and the absence of barriers on the excited-state surface. In particular, we have found that the electrocyclic closure and s-ciss-trans photochemical isomerization stops at 15 K for 2,3-dimethyl-1,3-butadiene-d10. The closure occurs at higher temperatures in solution but is slowed by a deuterium isotope effect. The s-trans conformer of EE-2,4-hexadiene shows almost no photoreactivity in a matrix under 254 nm irradiation, but the s-cis conformer is rapidly converted to ZE-2,4-hexadiene (ZE-HXD). The photoreactivity of ZE-HXD is similar in that there is a relatively quick conversion of the s-cis conformer under these conditions, with only a very slow conversion of the s-trans to photoproducts.

Michael Squillacote, Thomas Semple, JeWie Chen, and Fengting Liang "The Low-temperature Photochemistry of s-cis Acyclic 1,3-Dienes," Photochemistry and Photobiology 76(6), 634-639, (1 December 2002).<0634:TLTPOS>2.0.CO;2
Received: 5 July 2002; Accepted: 1 October 2002; Published: 1 December 2002

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