Photoinduced Coupling of Acetylenes and Quinone in the Solid State as Preorganized Donor−Acceptor Pairs
American Chemical Society
The Journal of Organic Chemistry
Crystalline electron donor−acceptor (EDA) complexes of various diarylacetylenes (DA) and dichlorobenzoquinone (DB) are isolated and structurally characterized by X-ray crystallography. Deliberate excitation of either the DB acceptor at λDB = 355 nm or the 1:2 [DA, 2DB] complex at λCT = 532 nm in the solid state leads to [2 + 2] cycloaddition and identical (isomeric) mixtures of the quinone methide products. Time-resolved (ps) diffuse reflectance spectroscopy identifies the ion-radical pair [DA•+, DB•-] as the reactive intermediate derived by photoinduced electron transfer in both photochemical procedures. The effects of crystal-lattice control on the subsequent ion-radical pair dynamics are discussed in comparison with the same photocouplings of acetylenes and quinone previously carried out in solution.