Clip-off Chemistry: Synthesis by Programmed Disassembly of Reticular Materials

Bond-breaking is an essential process in natural and synthetic chemical transformations. Accordingly, the ability for researchers to strategically dictate which bonds in a given system are broken translates to greater synthetic control, as historically evidenced in fields such as organic synthesis. Here, we report extending the concept of selective bond-breaking to reticular materials, in a new synthetic approach that we call Clip-off Chemistry. We show that bond-breaking in these structures can be controlled at the molecular level; is periodic, quantitative and selective; is effective in reactions performed in either solid or liquid phases; and can occur in a single-crystal-to-single crystal fashion involving the entire bulk precursor sample. Clip-off Chemistry opens the door to programmed disassembly of reticular materials and thus, to the design and synthesis of new molecules and materials.