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A Divergent Alkyne Diol Directs [2 + 2] Photoreactivity in the Solid State: Cocrystal, Supramolecular Catalysis, and
Shalisa M Oburn1, Jay Quentin1, Leonard R MacGillivray2
1Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA.
Abstract:
2-butyne-1,4-diol (1,4-bd) is used as a divergent ditopic template that directs trans-1,2-bis (n-pyridyl) ethylene (, where n = n' = 3 or 4) to undergo an intermolecular [2 + 2] photodimerization in the solid state. The components of cocrystals [(1,4-bd)·(4,4'-bpe)]n and [(1,4-bd)·(3,3'-bpe)]n form 1D hydrogen-bonded polymers with assembled as infinite parallel stacks. The alkenes undergo [2 + 2] photocycloadditions to form rctt-tetrakis (n-pyridyl) cyclobutane (where n = 3 or 4). We demonstrate that the reactive solid involving 4,4'-bpe exhibits supramolecular catalysis.
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In a chemical reaction, a relationship exists between the concentration of reactants and the rate at which the reaction proceeds. The study to measure this relationship is known as the kinetics of a chemical reaction. Kinetic studies are used to deduce the rate law of a chemical reaction, which provides information about the species involved during the transition state of the rate-determining step. Thus, kinetic studies help to derive the mechanism of a...

