Wavelength‐Controlled Dynamic Metathesis: A Light‐Driven Exchange Reaction between Disulfide and Diselenide Bonds

Wavelength‐controlled dynamic processes are mostly based on light‐triggered isomerization or the cleavage/formation of molecular connections. Control over dynamic metathesis reactions by different light wavelengths, which would be useful in controllable dynamic chemistry, has rarely been studied. Taking advantage of the different bond energies of disulfide and diselenide bonds, we have developed a wavelength‐driven exchange reaction between disulfides and diselenides, which underwent metathesis under UV light to produce Se−S bonds. When irradiated with visible light, the Se−S bonds were reversed back to those of the original reactants. The conversion of the exchange depends on the wavelength of the incident light. This light‐driven metathesis chemistry was also applied to tune the mechanical properties of polymer materials. The visible‐light‐induced reverse reaction was compatible with reductant‐catalyzed disulfide/diselenide metathesis, and could be utilized to develop a dissipative system with light as the energy input. Controlled metathesis: Metathesis between disulfide and diselenide bonds was realized under irradiation, and the conversion of the exchange reaction could be controlled by modulating the wavelength of the light. This chemistry was applied to polymer materials to control the cleavage of polymers from a distance.