Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation

Abstract

Design and synthesis of porous solids employing both reversible coordination chemistry and reversible covalent bond formation is described. The combination of two different linkage modes in a single material presents a link between two distinct classes of porous materials as exemplified by metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). This strategy, in addition to being a compelling material‐discovery method, also offers a platform for developing a fundamental understanding of the factors influencing the competing modes of assembly. We also demonstrate that even temporary formation of reversible connections between components may be leveraged to make new phases thus offering design routes to polymorphic frameworks. Moreover, this approach has the striking potential of providing a rich landscape of structurally complex materials from commercially available or readily accessible feedstocks.Teamwork saves the day when coordination chemistry and covalent bond formation can both occur in a single material. A balance between the incubation time of the organic components and solvent decomposition/base formation governs the competition between the two processes and determines the phase outcome. Even the temporary formation of reversible connections between components can be leveraged to make new phases.