Solid state H-1 NMR line-shape analysis and (double quantum) DQ H-1 NMR experiments have been used to investigate the segmental and polymer chain dynamics as a function of temperature for a series of thermosetting epoxy resins produced using different diamine curing agents. In these thermosets, chemical crosslinks introduce topological constraints leading to residual stresses during curing. Materials containing a unique ferrocene-based diamine (FcDA) curing agent were evaluated to address the role of the ferrocene fluxional process on the atomic-level polymer dynamics. At temperatures above the glass transition temperature (T-g), the DQ H-1 NMR experiments provided a measure of the relative effective crosslink and entanglement densities for these materials and revealed significant polymer chain dynamic heterogeneity in the FcDA-cured thermosets. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019