Effects of Substituents on Metastable-State Photoacids: Design, Synthesis, and Evaluation of their Photochemical Properties.

Recently, metastable-state photoacids have been widely used to control proton transfer in numerous chemical and biological processes as well as applications with visible light. Generally, substituents have a great influence on the photochemical properties of molecules, which will further affect their applications. Yet, the effects of substituents on metastable-state photoacids have not been studied systematically. In this work, 16 metastable-state photoacid derivatives were designed and synthesized on the basis of substituents having a large range of σ-π electron-donor-acceptor capabilities. The effects of substituents on the color display [or maximum absorption band(s)], solubility, pKa values, dark/photoacidity, photosensitivity, and relaxation kinetic(s) were investigated in detail. This study will be helpful for the targeted design and synthesis of promising photoacids and the application of their photocontrolled proton-release processes in functional materials/devices.