Photoinduced Coupling of Acetylenes and Quinone in the Solid State as Preorganized Donor−Acceptor Pairs

Authors

E. Bosch, University of Houston
S. M. Hubig, University of Houston
Sergey V. Lindeman, Marquette UniversityFollow
Jay K. Kochi, University of Houston

Document Type

Article

Language

eng

Publication Date

1998

Publisher

American Chemical Society

Source Publication

The Journal of Organic Chemistry

Source ISSN

0022-3263

Abstract

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 λ_DB = 355 nm or the 1:2 [DA, 2DB] complex at λ_CT = 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.

Comments

Accepted version. The Journal of Organic Chemistry, Vol. 63, No. 3 (1998): 592-601. DOI. © 1998 American Chemical Society. Used with permission.

Sergey V. Lindeman was affiliated with the University of Houston at the time of publication.

Recommended Citation

Bosch, E.; Hubig, S. M.; Lindeman, Sergey V.; and Kochi, Jay K., "Photoinduced Coupling of Acetylenes and Quinone in the Solid State as Preorganized Donor−Acceptor Pairs" (1998). Chemistry Faculty Research and Publications. 698.
https://epublications.marquette.edu/chem_fac/698