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

Abstract

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.

Tunable Structural Color Patterns Based on the Visible‐Light‐Responsive Dynamic Diselenide Metathesis

“…When introduced into material, the diselenide bond can be used for stress relaxation under visible light which endows materials with self‐healing,62 photo plasticity,63 3D topographical features,64 surface modification,65 etc. More importantly, the rate of diselenide metathesis could be adjusted by the wavelength of visible light 66. It proceeds more rapidly under the irradiation of light with a shorter wavelength 57.…”

Advanced functional polymer materials

“…In a recent study, Xu et al reviewed that Se-S bonds are also a dynamic covalent bond. 505 The dynamic metathesis between diselenide and disulfide could be manipulated by light at different wavelengths. Based on this, a disulfide and a diselenide containing PU were prepared with light-triggered attachable-cleavable behavior.…”

Strategies for Exploring Functions from Dynamic Combinatorial Libraries

“…[37] C) Decrease/increase the wavelength of input light signal to sequentially turn on/off the metathesis among SÀ S, SÀ Se and SeÀ Se bonds to manipulate the constitution of DCL. [38] into a supramolecular hydrogel, realizing a two-stage kinetic control.…”

“…In a parallel situation, Xu's group developed DCLs that utilizing different wavelengths to sequentially turn on/off the metathesis among SÀ S, SÀ Se and SeÀ Se bonds ( Figure 7C). [38] All the bonds were alive and commutative with each other under 280~390 nm UV-irradiation, which could also execute a program reset in the DCL at any time. Only SeÀ Se and SÀ Se bonds were effectively communicating under 410~500 nm irradiation, consuming SÀ Se bonds to amplify the kinetically trapped SÀ S bonds and the stoichiometrically accumulated SeÀ Se bonds.…”