Structural design, phase transition behavior, and ionic transport properties of state-independent electrolytes. (a) COEs show an abrupt conductivity drop at the fluid-solid transition, whereas SIEs maintain continuous Arrhenius behavior across phases. (b) SIE superstructure: mobile ions diffuse isotropically through an anisotropic columnar network of noncoordinating cations; positional and orientational order develops stepwise while alkyl chains remain flexible. (c) Electrostatic potential maps of SIEn⁺ versus imidazolium and ammonium cations, showing extensive charge delocalization and threefold symmetry. (d) POM images of SIE12·Cl as a crystal (C-I) at 40 °C and showing a characteristic Colhex liquid crystal texture at 61 °C. (e) Variable-temperature X-ray scattering patterns of SIE14·Cl, revealing differences in long- and short-range order across its Iso, LC, C-I, and C-II phases. The intensity in the d-range from ~6 to 15 Å is scaled up to visualize low-intensity peaks, with dashed lines overlaid to facilitate spectral comparison. (f) DC conductivity from the Iso to LC or C-I phases (n = 8, 10, 12, and 14 carbon atoms) shows continuous Arrhenius behavior; from Iso to the C-II phase (n = 16 and 18 carbon atoms) show a sharp drop. (g) MD simulations of Cl⁻ MSD in SIE10·Cl crystal under parallel and perpendicular fields, demonstrating isotropic ion transport. Adapted with permission from Ref. [7].