Tailoring van der Waals interactions in ultra-thin two dimensional metal-organic frameworks (MOFs) for...

The diverse structural tunability of 2-dimensional π-stacked layered metal-organic frameworks (2D MOFs) enables the control of charge carrier mobility to achieve specific photoconductive characteristics. This study demonstrates the potential of various theoretical methodologies and frameworks in establishing a correlation between structure and functionality for such purposes. Through a focus on the archetypal Ni₃(HITP)₂ 2D MOF, we examine the impact of quantum confinement and stacking fault defects on the absorption spectra using our recently-developed Frenkel-Holstein Hamiltonian. Specifically, the relationship between optical properties and number of layer units along the π-stacking direction is discussed. We employ Marcus rate theory to evaluate vertical carrier mobility subject to inter-layer proximity and different crystal packing which affect van der Waals interactions between layers. The insights presented in this research can inform the development of guidelines for enhancing photoconductive properties in 2D MOF nanosheets.