Design and Applications of Metastable-State Photoacids.

Proton transfer is one of the most common processes in nature, and many chemical, material, and biological processes are sensitive to proton concentration, from acid-catalyzed reactions to the activities of many enzymes. Photoacids that reversibly undergo proton dissociation upon irradiation promise remote spatial and temporal control over proton-sensitive processes and could provide a way to convert photoenergy into other types of energy. The recently discovered metastable-state photoacids can produce a large proton concentration with high efficiency and good reversibility. A reversible pH change of over 2 units has been demonstrated using an aqueous solution of a metastable-state photoacid. Additionally, moderate-intensity visible light, for example, from LEDs and sunlight, can be used to activate this type of photoacid. This photocontrolled proton release occurs in aqueous and nonaqueous solutions and in polymeric materials. Therefore, this type of photoacid can be conveniently incorporated into different systems to control various proton transfer processes. Metastable-state photoacids are generally designed by linking an electron-accepting moiety and a weakly acidic nucleophilic moiety with a double bond. Photoinduced trans-cis isomerization of the double bond allows a nucleophilic cyclization reaction to occur between the two moieties. The tandem reaction generates a highly acidic metastable form, which releases a proton. In the dark, the metastable form relaxes to the original form and takes back the proton. Several electron-accepting and nucleophilic moieties have been used to construct different types of metastable-state photoacids for different applications. The advantages and disadvantages of these photoacids in terms of their photoacidity, dark acidity, reversibility, stability, etc. will be discussed in this Account. Metastable-state photoacids have been used to catalyze bond formation and bond-breaking reactions in which the reactions can be activated and stopped by turning on and off irradiation, respectively. They have been used to reversibly protonate molecules to affect the ionic and hydrogen bonding between molecules or between different moieties of a molecule. Protonation can also alter the electronic configuration of molecules to change their electronic and optical properties. Since a proton has a positive charge, photoacids have been used to control ion exchange processes. Applying metastable-state photoacids to control Fisher esterification, volume-changing hydrogels, the killing of bacteria, odorant release, the color of materials, the formation of nanoparticles, and polymer conductivity has been reported by our group. Metastable-state photoacids have also been utilized to control supramolecular assemblies, molecular switches, microbial fuel cells, cationic sensors, nanoparticle aggregation, and ring-opening polymerizations. The future prospects of this research area will be discussed at the end of this Account.