AbstractThe molecular dynamics of a ferroelectric liquid crystal, denoted ZLL 7/*, is investigated by means of 2H NMR relaxation. The spin–lattice (T1Q and T1Z) and spin–spin (T2) relaxation times of two isotopomers of ZLL 7/*, labeled on the phenyl and biphenyl fragments, are measured and their behavior upon passing from the SmA to the hexatic phase, through the ferroelectric SmC*, antiferroelectric SmC*A, and re‐entrant ferroelectric SmC*re phases, is discussed. A comparison between the measured T2 and T2*, directly related to the experimental linewidth, provides information on the heterogeneity of the system, thus allowing confirmation of previous hypotheses concerning the structural and ordering properties of the SmC*A and SmC*re phases. The possibility to look at different sites of the core of the ZLL 7/* smectogen reveals a peculiar sensitivity of the phenyl moiety with respect to the biphenyl fragment, which may be justified by its vicinity to the chiral centers. Interestingly, the trend of the longitudinal relaxation times is characterized by a minimum that corresponds to the SmC*A and SmC*re phases, which is reproducible for the two isotopomers and at several Larmor frequencies. A quantitative analysis of T1Q and T1Z is performed in the SmA and SmC* phases, for which the narrowing regime approximation is valid. A multifrequency approach is applied to self‐consistently determine the diffusion coefficients for the overall molecular motions, namely spinning and tumbling, and the internal rotations around the para axes of the phenyl and biphenyl fragments. The effect of the magnetic field in unwinding the helical structure of the SmC* phase (for H>9 T) allows observation of a sensitive change in the rotational diffusion coefficients in the frustrated unwound SmC* phase with respect to the SmC* phase.