Establishing Design Rules through Coarse-Grained Simulations of Metal–Organic Framework Synthesis

The capabilities of coarse-grained simulations are applied to the modelling of two-dimensional Metal–Organic Framework (MOF) synthesis. The isoreticular chemistry of crystalline MOFs allows for modular and scalable reagents in synthesis, and furthermore, the simple nature of the synthesis allows for translation to coarse-grained simulations. The HOOMD-blue toolkit is used to construct the MOFs building blocks (metal nodes and organic linkers) from isotropic beads, retaining the basic symmetries of the molecular components. Lennard–Jones and Weeks–Chandler–Andersen pair potentials are used to model attractive and repulsive particle interactions, respectively. We analyze the crystallinity of the self-assembled products and explore the role of modulators—molecules that compete with the organic linkers in binding to the metal nodes to moderate the crystallization reaction—to explore the self-assembly mechanisms in defect-engineered MOFs.