Induced Production of Atypical Naturally Nonpreferred Metal–Organic Frameworks and Their Detachment via Provoking Post‐Mismatching

Abstract The structures of metal–organic frameworks (MOFs) are typically determined by the building blocks that compose them and the conditions under which they are formed. MOFs tend to adopt a thermodynamically and/or kinetically stable structure (naturally preferred form). Thus, constructing MOFs with naturally nonpreferred structures is a challenging task, as it requires avoiding the easier pathway toward a naturally preferred MOF. Herein, an approach to construct naturally nonpreferred dicarboxylate‐linked MOFs employing reaction templates is reported. This strategy relies on the registry between the surface of the template and the cell lattice of a target MOF, which reduces the effort required to form naturally nonpreferred MOFs. Reactions of p‐block trivalent metal ions (Ga³⁺ and In³⁺) with dicarboxylic acids typically produce preferred MIL‐53 or MIL‐68. However, the surface of UiO‐67 (and UiO‐66) template exhibits the well‐defined hexagonal lattice, which induce the selective formation of a naturally nonpreferred MIL‐88 structure. Inductively grown MIL‐88s are purely isolated from the template via provoking a post‐mismatch in their lattices and weakening the interfacial interaction between product and template. It is also discovered that an appropriate template for effective induced production of naturally nonpreferred MOFs shall be properly selected based on the cell lattice of a target MOF.