Two-Dimensional Metal–Organic Framework Self-Assembly and Defect Engineering Studied via Coarse-Grained Simulations

• Published in: Chemistry of materials 2023-12, Vol.35 (23), p.10050-10059
• Main Authors: Scott, Reum N., Frank, Claire E., Martirossyan, Maya M., Milner, Phillip J., Dshemuchadse, Julia
• Format: Article
• Language: English
• ISSN: 0897-4756; 1520-5002
• DOI: 10.1021/acs.chemmater.3c02049

Metal–organic frameworks (MOFs) are crystalline materials that self-assemble from inorganic nodes and organic linkers, and isoreticular chemistry allows for modular and synthetic reagents of various sizes. In this study, a MOF’s componentsmetal nodes and organic linkersare constructed in a coarse-grained model 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, and which we construct analogouslyduring the self-assembly process of defect-engineered MOFs. The coarse-grained simulation allows for the uncoupling of experimentally interdependent variables to broadly map and determine essential MOF self-assembly conditions, among which are properties of the modulator: binding strength, size (steric hindrance), and concentration. Of these, the simulated modulator’s binding strength has the most pronounced effect on the resulting MOF’s crystal size.