Thermolabile Groups in Metal-Organic Frameworks: Suppression of Network Interpenetration, Post-Synthetic Cavity Expansion, and Protection of Reactive Functional Groups

Creating nothing out of something: A bulky tert‐butoxycarbonyl group on a biphenyl‐4,4′‐dicarboxylate ligand suppresses interpenetration to give an open, cubic metal–organic framework. Post‐synthetic cleavage of this group by simple thermolysis (see picture) unmasks a potentially reactive amino functional group, increases the void space (yellow sphere), and widens the pore apertures.