Journal
ACS MACRO LETTERS
Volume 11, Issue 2, Pages 264-269Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsmacrolett.1c00795
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Funding
- National Natural Science Foundation of China [21971177, 21774080]
- Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions
- Program of Innovative Research Team of Soochow University and Postgraduate Research & Practice Innovation Program of Jiangsu Province [KYCX21_2941]
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In this study, a polarization-induced metathesis mechanism for diselenides under heating conditions in the dark is proposed. Experimental results support that the exchange reaction of diselenides does not involve any radicals and is influenced by solvent polarity and the introduction of polar groups. DFT calculations also demonstrate that polarity has a significant effect on the heterolytic bond dissociation energies. The experimental results for allyl selenide small molecules, polymers, and polymer materials catalyzed by diselenide further confirm the polarization-induced metathesis mechanism.
Diselenide, as a dynamic covalent bond, has been widely applied in functional materials due to its response to light, heat, sonication, pH, and other stimuli. Herein, a polarization-induced metathesis mechanism for diselenides under heating conditions in the dark is proposed. First, a radical trap experiment is used to prove that the exchange reaction of diselenides in the dark does not involve any radicals. Second, the dynamic exchange reaction of diselenides is found to be affected not only by the polarity of the solvent but also by the introduction of polar groups into the molecular skeleton. Furthermore, DFT calculations also support the notion that polarity has a large effect on the heterolytic rather than homolytic bond dissociation energies. The experimental results for allyl selenide small molecules, polymers, and polymer materials catalyzed by diselenide all support the polarization-induced metathesis mechanism. In short, we successfully enhanced the understanding of the mechanism for diselenide metathesis.
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