Crystallization-Induced Dimerization and Solution-Phase Bond Dissociation of Stable Dibenzoolympicenyl Radicals.

Autor: Zhang X; Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin, 300072, P. R. China., He H; Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin, 300072, P. R. China., Ge C; Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin, 300072, P. R. China., Xiang Q; Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin, 300072, P. R. China., Sato S; 'Integrated Molecular Structure Analysis Laboratory', Department of Applied Chemistry School of Engineering, The University of Tokyo, 6-6-2 Kashiwanoha, Kashiwa-shi, Chiba, 277-0882, Japan.; Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi, 444-8787, Japan., Lv M; Engineering Research Center for Energy Conversion and Storage Technology of Guizhou, School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, 550025, China., Chen X; Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin, 300072, P. R. China., Sun Z; Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin, 300072, P. R. China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 07, pp. e202418261. Date of Electronic Publication: 2024 Oct 07.
DOI: 10.1002/anie.202418261
Abstrakt: Crystallization of organic materials can lead to different assembly structure with different reactivity, but this phenomenon is rarely observed for delocalized hydrocarbon radicals. This report introduces a crystallization-induced radical-radical coupling reaction, which employs a series of stable nonplanar organic π-radicals as reactants. Six stable radical congeners are synthesized, resulting in radical-radical coupling at the allenyl radical site during crystallization to produce close-shell dimers. This coupling reaction is absent in the solution phase, which highlights the importance of preorganization in the lattice. Remarkably, the attempts of cocrystallization of different congeners yielded homocoupling products instead of cross-coupling products. In specific cases, two distinct polymorphs are observed and their reactivity is different according to the distance of the reaction sites. Theoretical calculations indicate that the transition from a metastable preorganized monomer to a dimer is barrierless and spontaneous. The dimer could regenerate free radicals by heating or photoirradiation in the solution phase. This discovery may lead to controllable molecular switches.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: