Synthesis of Metal–Organic Cages via Orthogonal Bond Cleavage in 3D Metal–Organic Frameworks
Sara Ruiz‐Relaño, Dongsik Nam, Jorge Albalad, Alba Cortés‐Martínez, Judith Juanhuix, Inhar Imaz, Daniel Maspoch
Abstract
Herein we address the question of whether a supramolecular finite metal-organic structure such as a cage or metal-organic polyhedron (MOP) can be synthesized via controlled cleavage of a three-dimensional (3D) metal-organic structure. To demonstrate this, we report the synthesis of a Cu(II)-based cuboctahedral MOP through orthogonal olefinic bond cleavage of the cavities of a 3D, Cu(II)-based, metal-organic framework (MOF). Additionally, we demonstrate that controlling the ozonolysis conditions used for the cleavage enables Clip-off Chemistry synthesis of two cuboctahedral MOPs that differ by their external functionalization: one in which all 24 external groups represent a mixture of aldehydes, carboxylic acids, acetals and esters, and one in which all are aldehydes.