title: The low-temperature photochemistry of s-cis acyclic 1,3-dienes.
abstract: 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-cis-s-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.
authors.affiliation: Department of Chemistry, Auburn University, Auburn, AL 36849, USA. squilme@auburn.edu
authors.forename: Michael
authors.initials: M
authors.lastname: Squillacote
authors.forename: Thomas
authors.initials: T
authors.lastname: Semple
authors.forename: JeWie
authors.initials: J
authors.lastname: Chen
authors.forename: Fengting
authors.initials: F
authors.lastname: Liang