Maximizing the Carrier Mobilities of Metal-Organic Frameworks Comprising Stacked Pentacene Units

Charge transport properties of metal-organic frameworks (MOFs) are of distinct interest for (opto)electronic applications. In contrast to the situation in molecular crystals, MOFs allow an extrinsic control of the relative arrangement of Jr-conjugated entities through the framework architecture. This suggests that MOFs should enable materials with particularly high through-space charge carrier mobilities. Such materials, however, do not yet exist, despite the synthesis of MOFs with, for example, seemingly ideally packed stacks of pentacene-bearing linkers. Their rather low mobilities have been attributed to dynamic disorder effects. Using dispersion-corrected density functional theory calculations, we show that this is only part of the problem and that targeted network design involving comparably easy-to-implement structural modifications have the potential to massively boost charge transport. For the pentacene stacks, this is related to the a priori counterintuitive observation that the electronic coupling between neighboring units can be strongly increased by increasing the stacking distance.

Automated summary

MOFs offer the potential to create materials with high charge carrier mobilities by controlling the arrangement of Jr-conjugated entities, but current results are still unsatisfactory. Research shows that targeted network design and structural modifications have the potential to significantly enhance charge transport properties.