Planar Metal-Organic Frameworks (MOFs) with extended two-dimensional (2D) π-conjugation and graphene-like structures are currently among the most conductive frameworks known. The confinement of charge carriers within the 2D lattice forces charge transport in the direction of the plane due to improved conjugation and enhanced p-d orbital coupling. Structurally tuneable bandgap and possibility for unique magnetic exchange interactions as well as their large surface area and penetrability for targeted analytes make 2D MOFs perfect options for catalytic applications in (photo)electrochemical devices. In spite of these merits, engineering of targeted structure-property relationships in 2D MOFs remains a challenge due to limited fundamental understanding of intrinsic MOF structure and the effect of the surrounding and/or confined water on the charge mobility and charge transfer at host-guest interfaces within MOFs. For example, while an aqueous environment allows formation of a slipped parallel stacking of Cu 3 (HHTP) 2 (H 2 O) 6 (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) layers, substitution of Cu(II) to Ni(II) or Co(II) results in partial hydrolysis of metal-ligand bonds and creation of an alternative stacking mode of M 3 (HHTP) 2 (H 2 O) 6 and M 3 (HHTP)(H 2 O) 12 layers. Here, we build a theoretical framework for studying the effect of surrounding and confined water molecules on the electronic properties of a family of 2D conductive MOFs with the general formulae of M 3 (HTTP) 2 (H 2 O) 6 (M=Cu 2+ , Co 2+ , and Ni 2+ , HTTP=2,3,6,7,10,11-hexathiotriphenylene). We build the initial structures of these MOFs using the only crystallographic data available for 2D MOFs related to Co 3 (HHTP) 2 (HHTP=2,3,6,7,10,11- hexahydroxytriphenylene) and removing the alternating hydrolyzed layer. Then, running periodic electronic structure calculations, we study the effect of different metal centers on the geometrical and electronic properties of these MOFs. We study the effect of water dynamics with performing ab initio molecular dynamics simulations on frozen optimized frameworks and different loadings of water molecules. Finally, to account for dynamical hydrogen-bond network of outer layers of water and its effect on interfacial charge transfer, we adopt a Quantum Mechanics (QM)/Molecular Mechanics (MM) framework where water molecules of the outer solvation shells are described via iAMOEBA polarizable quantum water potential model.

Theoretical insights into electronic properties of 2D conductive metal-organic frameworks in the presence of surrounding and confined water molecules

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.