Despite a relatively small change in the total in-pore anion population on charging, it was possible to detect more subtle charging processes by monitoring the chemical shift of the in-pore environment. It was found that the in-pore chemical shift in both electrolytes was strongly correlated with the charge stored in the electrode, giving rise to a linear relationship (Figure ). We propose that this variation of the Δδ value is related to changes in both the distribution of anions between pore-centre and pore-edge sites (which are expected to be in fast exchange on the NMR timescale) and the strength of the specific interaction between the anion and the MOF N-H sites. Further QM/MM simulations with charging were used to investigate this behaviour (Figure , SI Table ). On negative charging (Figure , bottom left), a dramatic change in anion distribution is observed relative to the uncharged scenario (Figure , bottom middle), with a significant shift in anions towards the pore centre. This can be attributed to the now less favourable interactions with the net negative MOF pore edge. The drop in anion population at the pore edge site is indicated by the reduced integral of the peak around 5 Å in the radial distribution function (Figure , top middle). Any anions remaining close to the pore edge will also experience a weaker H-bonding interaction owing to a smaller partial positive charge on the H atom of the MOF N-H groups, and this is amplified by a shift of the pore-edge environment away from the MOF walls also seen in the radial distribution function, with the peak around 5 Å shifting to a greater rB-Ni distance (Figure , top middle). These synergistic effects lead to a reduced Δδ value during negative charging. Conversely, on positive charging (Figure , bottom right), the anions interact more favourably with the edge of the MOF, where the N-H groups become more positively charged, and so anions migrate towards the pore boundary of the MOF, resulting in a higher pore-edge population in closer proximity to the N-H groups (Figure , top middle). Therefore, an increase in the average Δδ value is observed. A similar behaviour of anion rearrangements has previously been proposed in the related MOF, Cu3(HHTP)2. These experimental observations were found to be in qualitative agreement with calculated F chemical shift values with charging of a MOF fragment using implicit solvation of an adsorbed BF4 -anion (SI Figure ). Therefore, whilst the total in-pore anion population is almost invariant as cations dominate the charge storage for these conductive layered MOF systems, NMR has the power to track subtle changes in the anion distribution within the pore structure and the strength of the MOF-electrolyte interaction.