Switching the Proton Conduction in Nanoporous, Crystalline Materials by Light

Abstract Proton conducting nanoporous materials attract substantial attention with respect to applications in fuel cells, supercapacitors, chemical sensors, and information processing devices inspired by biological systems. Here, a crystalline, nanoporous material which offers dynamic remote‐control over the proton conduction is presented. This is realized by using surface‐mounted metal–organic frameworks (SURMOFs) with azobenzene side groups that can undergo light‐induced reversible isomerization between the stable trans and cis states. The trans – cis photoisomerization results in the modulation of the interaction between MOF and guest molecules, 1,4‐butanediol and 1,2,3‐triazole; enabling the switching between the states with significantly increased ( trans ) and reduced ( cis ) conductivity. Quantum chemical calculations show that the trans ‐to‐ cis isomerization results in the formation of stronger hydrogen bridges of the guest molecules with the azo groups, causing stronger bonding of the guest molecules and, as a result, smaller proton conductivity. It is foreseen that photoswitchable proton‐conducting materials may find its application in advanced, remote‐controllable chemical sensors, and a variety of devices based on the conductivity of protons or other charged molecules, which can be interfaced with biological systems.