Abstract
Bond breaking is an essential process in chemical transformations and the ability of researchers to strategically dictate which bonds in a given system will be broken translates to greater synthetic control. 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. We validate Clip‐off Chemistry by synthesizing two topologically distinct 3D metal‐organic frameworks (MOFs) from two reported 3D MOFs, and a metal‐organic macrocycle from metal‐organic polyhedra (MOP). Clip‐off Chemistry opens the door to the programmed disassembly of reticular materials and thus to the design and synthesis of new molecules and materials.
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