New dynamic bonds using Ru-ligand coordination for photoresponsive materials
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Abstract
Photodynamic bonds are stable in the dark but reversibly dissociate/form under light irradiation. Photodynamic bonds are promising building blocks for responsive or healable materials, photoactivated drugs, nano-carriers, extracellular matrices, etc. However, reactive intermediates from photodynamic bonds usually lead to side reactions, which limit their application.
Here, I found that the Ru-Se coordination bond is a photodynamic bond that reversibly dissociates under mild visible light irradiation conditions (chapter 2). I observed that Ru-Se bonds form via the coordination of a selenoether ligand with [Ru(tpy)(biq)(H2O)]Cl2 (tpy = 2,2’:6’,2”-terpyridine, biq = 2,2’-biquinoline) in the dark, while the Ru-Se bond dissociates reversibly under visible light irradiation. No side reaction was detected in the formation and dissociation of Ru-Se bonds.
In chapter 3, I demonstrate that the Ru-Se bond is applicable to different operating environments. Therefore, I prepared photoresponsive amphiphiles, surfaces, and polymer gels using Ru-Se bonds. The amphiphiles with Ru-Se bonds showed reversible morphological transitions between spherical micelles and bowl-shaped assemblies in dark/light irradiation cycles. The surfaces modified with Ru-Se-bond-containing compounds showed photoswitchable wettability. Polymer gels with Ru-Se crosslinks underwent photoinduced reversible sol-gel transitions, which were used for reshaping and healing. These results demonstrate that the Ru-Se bond is a new dynamic bond for constructing responsive, reprocessable, switchable, and healable materials that work in a variety of environments.