Lewis Acid‐Mediated Radical Stabilization and Dynamic Covalent Bonding: Tunable, Reversible and Photocontrollable

Author:

Liu Min1,Yang Xing2,Sun Quanchun1,Wang Tao1,Pei Runbo1,Yang Xingyu1,Zhao Yue1,Zhao Lili2ORCID,Frenking Gernot23ORCID,Wang Xinping1ORCID

Affiliation:

1. State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210023 China

2. Institute of Advanced Synthesis School of Chemistry and Molecular Engineering Jiangsu National Synergetic Innovation Center for Advanced Materials Nanjing Tech University Nanjing 211816 China

3. Fachbereich Chemie Philipps-Universität Marburg Hans-Meerwein-Strasse 4 35032 Marburg Germany

Abstract

AbstractThis work describes a strategy not only to isolate a dynamically stable radical with physical property tunability, but to efficiently regulate the radical dissociation with reversibility and photo controllability. The addition of Lewis acid B(C6F5)3 (BCF) into the solution of a radical σ‐dimer (1‐1) led to a stable radical (1⋅‐2B), which has been characterized by EPR spectroscopy, UV/Vis spectroscopy and single crystal X‐ray diffraction, in conjunction with theoretical calculation. The radical species is stabilized mainly by captodative effect, single electron transfer and steric effect. The absorption maximum of the radical can be tuned by using different Lewis acids. Dimer 1‐1 can be achieved back by addition of a stronger base into the solution of 1⋅‐2B, exhibiting a reversible process. By introducing a photo BCF generator, the dissociation of the dimer and the formation of the radical adduct become photocontrollable.

Funder

National Natural Science Foundation of China

Nanjing Tech University

Publisher

Wiley

Subject

General Medicine

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