Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 114, Issue 27, Pages 7377-7381Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp101703q
Keywords
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Funding
- Israel Science Foundation [499/08]
- US National Science Foundation [CHE0843922]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0843922] Funding Source: National Science Foundation
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The [4 + 4] photodimerization of 1,4-dimethyl-2-pyridinone (A) in its molecular compound with 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol (1) was investigated by irradiation of a single crystal of the compound. The conversion to the product in a single-crystal to single-crystal transformation enabled the determination of its crystal structure after each exposure cycle of 10-20 min with a pulsed 355 nm laser light. The unit cell changes as a function of the conversion were monitored and showed monotonic changes. The kinetics of the reaction was studied at two different temperatures (230 and 280 K) and revealed a sigmoidal behavior that could be explained by the JMAK model for crystal growth with a mechanism that is intermediate between random distribution of products in the crystal and the existence of growing nuclei. The Arrhenius plot provided calculated activation energy of 32.5 kJ/mol.
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