Reversible and irreversible chemisorption in nonporous-crystalline hybrids.

The tools of synthetic chemistry allow us to fine-tune the reactivity of molecules at a level of precision not yet accessible with inorganic solids. We have investigated hybrids that couple molecules to the superior thermal and mechanical properties of solids. Herein we present, to the best of our knowledge, the first demonstration of reactivity between hybrid perovskites and substrates. Reaction with iodine vapor results in a remarkable expansion of these materials (up to 36 % in volume) where new covalent CI bonds are formed with retention of crystallinity. These hybrids also show unusual examples of reversible chemisorption. Here, solid-state interactions extend the lifetime of molecules that cannot be isolated in solution. We have tuned the half-lives of the iodinated structures from 3 h to 3 days. These nonporous hybrids drive substrate capture and controlled release through chemical reactivity. We illustrate the strengths of the hybrid by considering radioactive iodine capture.