We first consider the molecular electrostatic potential on the 0.001 au electron density isosurface of RM734 (Fig. ); this shows alternating regions of electronegativity/electropositivity that result from the esters/nitro and alkyl/aryl units, respectively. In complexes 1 and 2 these regions of opposite potential are retained, and augmented by large charges localised around the pyridinium-carboxylate portion. The importance of these alternating regions of positive and negative electrostatic potential is not entirely clear, however it can be envisioned that the alternating ESP charges give rise to relatively strong electrostatic interactions between adjacent molecules. Simple inspection of the isosurface data reveals that the terminal CH3 and NO2 groupsboth of which are found in RM734 and also 1/2 -have the largest electropositivity/negativity respectively, presenting a clear route to polar head-to-tail pair formation. We consider that these strong electrostatic interactions most likely contribute to emergent polar order in conjunction with dipole-dipole interactions, by favouring (slightly) the formation of parallel over antiparallel pairs through some sort of biasing steric pressure. In future, it might perhaps be desirable to utilise the electronegativity of the pyridine nitrogen atom to contribute towards the electric dipole moment of the molecule rather than working against it as it does here. We have synthesised the 4-nitro-3-pyridyl analogues of RM734 and related materials (most of which display enhanced NF phase stability relative to the progenitor material) and investigation of their resulting complexes is one direction for future research. Equally, we do not expect supermolecular NF materials to be restricted to the H-bond donor (carboxylic acid) and acceptor (pyridine) combination detailed here, and complexes formed by other strong non-covalent interactions such as halogenbonding (e.g. pyridine + iodinemonochloride) also appear worthy of investigation.