Abstract
In recent years, charge transport in metal-organic frameworks (MOFs) has shifted into the focus of scientific research. In this context, systems with efficient through-space charge transport pathways resulting from π-stacked conjugated linkers are of particular interest. In the current manuscript, we use density functional theory-based simulations to provide a detailed understanding of such MOFs, which, in the present case, are derived from the prototypical Zn(2)(TTFTB) system (with TTFTB(4-) corresponding to tetrathiafulvalene tetrabenzoate). In particular, we show that factors such as the relative arrangement of neighboring linkers and the details of the structural conformations of the individual building blocks have a profound impact on bandwidths and charge transfer. Considering the helical stacking of individual tetrathiafulvalene (TTF) molecules around a screw axis as the dominant symmetry element in Zn(2)(TTFTB)-derived materials, the focus, here, is primarily on the impact of the relative rotation of neighboring molecules. Not unexpectedly, changing the stacking distance in the helix also plays a distinct role, especially for structures which display large electronic couplings to start with. The presented results provide guidelines for achieving structures with improved electronic couplings. It is, however, also shown that structural defects (especially missing linkers) provide major obstacles to charge transport in the studied, essentially one-dimensional systems. This suggests that especially the sample quality is a decisive factor for ensuring efficient through-space charge transport in MOFs comprising stacked π-systems.