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Chemical principles for electroactive metal–organic frameworks

  • Metal–Organic Frameworks for Electronics and Photonics
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Abstract

Metal–organic frameworks (MOFs) are porous ordered arrays of inorganic clusters connected by organic linkers. The compositional diversity of the metal and ligand, combined with varied connectivity, has yielded more than 20,000 unique structures. Electronic structure theory can provide deep insights into the fundamental chemistry and physics of these hybrid compounds and identify avenues for the design of new multifunctional materials. In this article, a number of recent advances in materials modeling of MOFs are reviewed. We present the methodology for predicting the absolute band energies (ionization potentials) of porous solids as compared to those of standard semiconductors and electrical contacts. We discuss means of controlling the optical bandgaps by chemical modification of the organic and inorganic building blocks. Finally, we outline the principles for achieving electroactive MOFs and the key challenges to be addressed.

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Acknowledgments

We thank W. Kohn and H. Kroto for the development of density functional theory and physical properties of MOF chemistry, respectively, as well as for stimulating lectures and discussions on these topics. The research discussed here has benefited from collaboration with J.K. Bristow, D. Tiana, and K.L. Svane. We acknowledge support from The Royal Society, the European Research Council (Grant No. 27757) and the EPSRC (Grant No. EP/M009580/1 and EP/K016288/1). This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation Grant Number ACI-1053575.

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Authors and Affiliations

  1. Department of Materials, Imperial College London, UK

    Aron Walsh

  2. Department of Chemistry, University of Bath, UK

    Keith T. Butler

  3. Department of Chemistry, Massachusetts Institute of Technology, USA

    Christopher H. Hendon

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Walsh, A., Butler, K.T. & Hendon, C.H. Chemical principles for electroactive metal–organic frameworks. MRS Bulletin 41, 870–876 (2016). https://doi.org/10.1557/mrs.2016.243

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