Ligand field tuning of d-orbital energies in MOF clusters
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Date
2023-04-12
Authors
Diamond, Brian
Payne, Lillian
Hendon, Christopher
Journal Title
Journal ISSN
Volume Title
Publisher
Research Square
Abstract
Linker functionalization is a common route used to affect the electronic and catalytic properties of
metal-organic frameworks. By either pre- or post-synthetically installing linkages with differing
linker moieties the band gap, workfunction, and exciton lifetimes have been shown to be affected.
One overlooked aspect of linker functionalization, however, has been the impact on the metal dorbital
energies to which they are bound. The ligand field differences should result in substantial
changes in d-splitting. In this study we use DFT to study the energetics of d-orbital energy tuning
as a function of linker chemistry. We offer a general descriptor, linker pKa, as a tool to predict the
resultant d-splitting in MOFs. Our calculations reveal that simple functionalizations can affect the
d-energies by up to 2 eV and illustrate the significance of this band modularity using four
archetypal MOFs: UiO-66, MIL-125, ZIF-8, and MOF-5. Together, we show that linker
functionalization dramatically affects d-energies in MOF clusters and highlight that linker
functionalization is a useful route for fine-tuning band edges centered on the metals, rather than
linkers themselves.
Description
20 pages
Keywords
d-energies, Metal-organic frameworks
Citation
Diamond, B., Payne, L., & Hendon, C. (2023). Ligand field tuning of d-orbital energies in MOF clusters. Research Square, 1—20. https://doi.org/10.21203/rs.3.rs-2416561/v1