Ferroelectric materials exhibit a spontaneous and switchable polarisation arising from the alignment of electric dipoles with an applied electric field. In most ferroelectrics, the atomic mechanism involves dipoles that are correlated below a symmetry-breaking phase transition: this includes both the displacive transitions common amongst ceramics, such as the widely industrially used BaTiO3, and order-disorder transitions in the hydrogen-bonded ferroelectrics Rochelle's salt and K2HPO4, which are built from molecular units. These phase transitions are associated with a sharp discontinuity in the dielectric permittivity as a function of temperature. On the other hand, relaxor ferroelectrics have broad peaks in their temperature dielectric spectra, with the peak temperature depending significantly on frequency; most such materials are ceramic or organic polymer based systems that show no bulk symmetry change in the temperature range in which their dielectric constants peak. Relaxor ferroelectrics are desirable materials for harvesting waste mechanical energy, high power energy storage in capacitors and ultrasound sensing applications, due to their large dielectric constants and piezoelectric responses. In addition, the broad temperature range over which they exhibit their high dielectric responses offers a wider operational window for functional devices. Common drawbacks of such materials are that they are usually Pb based (and many lead-free alternatives still contain heavy metals) and most suffer electromechanically induced strain. In established families of relaxor ferroelectrics, the relaxor behaviour is almost ubiquitously associated with compositional inhomogeneity. For example, ceramic oxide relaxors are usually perovskites with a complex mixture of positionally disordered cations on their A and B sites; while in wholly organic polymer relaxors, inhomogeneity is achieved through a distribution of different functional groups. This gives rise to a domain structure associated with the temperature and frequency dependence of the dielectric properties. There has been much recent interest in hybrid ferroelectrics, comprised of both inorganic and organic components. Several such materials show dielectric spectra characteristic of relaxor behaviour. Unlike known relaxors, however, these inorganic-organic hybrid ferroelectric materials are not doped and show no compositional disorder (similar behaviour has also been reported in a homogeneous molecular organic solid ). The origin of the relaxor-like properties in these materials therefore remains unclear. We have recently highlighted that the relaxor-like dielectric properties of [NH3NH2]Mg(HCO2)3 are likely caused by the polar phase featuring a mixture of NH3NH2 + cations that are perpendicular and parallel to the channel. The populations appear to interchange in the polar phase, with this orientational disorder giving rise to fluctuating regions of polar NH3NH2 + cations aligned along the channels in a matrix of nonpolar NH3NH2 + cations perpendicular to the channels. This study utilised a mixture of neutron single crystal diffraction, 2 H NMR and quasi-elastic neutron scattering, which have particular sensitivity to the cation behaviour across a range of timescales through their sensitivity to hydrogen. Here, we have employed a similar multi-technique methodology to gain a deeper understanding of the origins of the more limited dielectric relaxation in the [NH4]M(HCO2)3 frameworks, which adopt a similar chiral hexagonal structure. Given indications that the size of the B-site cation has a significant effect on the ferroelectric transition, we have focused on the Mn 2+ and Zn 2+ members of the series, which have the smallest and largest cation known to undergo the ferroelectric-paraelectric phase transition.