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Cascade Photoreaction in Crystals: A Phase Change Caused by a Dewar Benzene Quantum Chain Triggers a Topochemical [2 + 2] Photodimerization

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Crystals undergoing tandem reactions where the first transformation enables the second one are rare. Using photoreactive Dewar benzene 3,4,5,6-tetramethyl-1,2-dicarboxylic diacid ( DB ) as a hydrogen-bonding template for the [2π+2π] photodimerization of trans -4,4′-bipyridyl-ethenes ( BPE ), we obtained crystals DB-BPE-NT with a DB:BPE = 2:1 stoichiometry with double bonds at a nonreactive distance of 5.957 Å. Exposure to UV light resulted in valence bond isomerization to Hückel benzene 3,4,5,6-tetramethyl-1,2-dicarboxylic acid ( HB ) by a quantum chain reaction that triggered the sought-after topochemical [2π+2π] photodimerization reaction. Notably, crystals HB:BPE-T with the Hückel benzene isomer and BPE adopted a 2:2 stoichiometry and displayed an efficient topochemically templated photodimerization reaction.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c09377

Authors: Indrajit Paul, Krzysztof A. Konieczny, Roberto Chavez, Jing-Ran Shan, Kendall N. Houk, Miguel A. Garcia-Garibay

Institutions: University of California, Los Angeles, Wrocław University of Science and Technology

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: National Science Foundation, Division of Chemistry