Two-dimensional (2D) conductive metal-organic frameworks (MOFs) are a unique class of porous materials which offer electrical conductivity along with large surface area and penetrability for targeted analytes, making them perfect options for catalytic applications in (photo)electrochemical water splitting as well as electrical energy storage. 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 its electronic properties, and limited knowledge of charge mobility and charge transfer at host-guest interfaces within MOFs. Here, we take up this challenge through rigorous computational modelling and dynamical simulations. We build the initial structure of a copper-based 2D MOF using the only crystallographic data available for 2D MOFs related to Co3(HHTP)2(H2O)6 (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene). Then, running periodic electronic structure calculations, we study the effect of different organic ligand substitutions, HHTP, HITP (hexaiminotriphenylene), and HTTP (hexathiotriphenylene), on the geometrical and electronic properties of these copper-based MOFs. The ligand substitution results in interesting variations in both geometry and electronic properties of 2D MOFs, changing the hybridization of metal center all the way from semi-square planer to tetrahedral and distorting the 2D sheets to different degrees. By building only one layer of these 2D MOFs and repeating periodic calculations only in XY directions, we distinguish and discuss the intra vs inter-layer charge transfer pathways. To carry out a detailed quantum dynamical study, we use charge densities of key states to localize electrons and holes following band gap excitation. Then, we utilize nonadiabatic quantum dynamics simulations (surface-hopping) for studying electron-hole separation and/or recombination. These insights into the energy relaxation and electron-hole recombination processes are valuable for investigating photocatalytic activity of M3(H(H,I,T)TP)2(H2O)6 MOFs in general.

Effect of ligand substitution on nonadiabatic dynamics of charge carriers in 2D conductive metal-organic frameworks

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.