Clip‐off Chemistry: Synthesis by Programmed Disassembly of Reticular Materials**

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.

Fluorescence microscopy imaging of a neurotransmitter receptor and its cell membrane lipid milieu

“…Similarly the concept of “clip” or “clip-off” chemistry is associated with the ability to cleave covalent bonds and thus “sculpt” or etch the composition of the molecules ( Shieh et al, 2021 ). The latter approaches comprise a variety of techniques to introduce cleavable groups in molecules, labilize linkers, break only selected chemical bonds in the molecular lattice, and tailor the structures to produce new molecules that depart from the original ones in topology or properties, while retaining dimensionality ( Yang et al, 2022 ). SnAP chemistry is usually applied to the synthesis of medium-ring (6-9 membered) saturated N-heterocycles, including bicyclic and spirocyclic structures.…”

Isoreticular Contraction of Metal–Organic Frameworks Induced by Cleavage of Covalent Bonds

“…Herein, we report a new approach to isoreticular contraction of MOFs that is based on breaking of covalent bonds and does not require addition of any external linkers (Figure ). Recently, we described clip-off chemistry, a new synthetic strategy to make new molecules and materials based on the selective, quantitative, and controlled cleavage of bonds in reticular materials . Here, we show that this concept can be applied to control the stepwise synthesis of isoreticular MOFs exhibiting contracted structures relative to their parent MOFs.…”

Material Design and Reticular Chemistry: Unveiling New Topologies through Face Decoration of Edge Nets

“…When it comes to synthesis, trial error approach certainly contributed to a considerable fraction of the 114,373 structures contained in the Cambridge Structural Database MOF subset . However, understanding both the chemistry and geometry fundamentals that allow the formation, in situ , of a specific inorganic cluster with predicted connectivity and directionality (points of extension) is an additional requirement for those who aim to rationally assemble materials …”

“…27 However, understanding both the chemistry and geometry fundamentals that allow the formation, in situ, of a specific inorganic cluster with predicted connectivity and directionality (points of extension) is an additional requirement for those who aim to rationally assemble materials. 28 Many network topologies (nets) have been identified and reported within periodic materials (zeolites, MOFs, COFs•••), 29−31 and millions more have been predicted. 32,33 Zeolitic nets are highly relevant as they have the particularity to make a bridge between zeolites and MOFs, gathering the best of these two types of porous materials into zeolite-like MOFs (ZMOFs).…”