Deciphering supramolecular and polymer-like behavior in metallogels: real-time insights into temperature-modulated gelation and rapid self-assembly dynamics

Bis(pyridyl) urea-based gelators, namely L2 and its isomeric mixture (L1 + L2), are known to self-assemble into 1D architectures capable of inducing supramolecular gelation. Coordination with metal ions such as Ag(i), Cu(ii), and Fe(iii) introduces structural reinforcement, enabling the formation of distinct 3D networks governed by metal-specific coordination geometries. Here, we present a comprehensive investigation into the temperature-responsive behavior (20-60 °C) of L2 and L1 + L2, both in the absence and presence of Ag(i), Dy(iii), Fe(iii), Cu(ii), and Ho(iii), using real-time small-angle neutron scattering (SANS). To probe long-term structural evolution/kinetics of self-assembly, real-time small-angle X-ray scattering (SAXS) was employed on L2 + Ag gels, complemented by differential scanning calorimetry (DSC) to evaluate thermal transitions. Our results reveal strikingly divergent gelation behaviors: L2 forms a highly rigid, covalent polymer-like network, while L1 + L2 exhibits remarkable thermal adaptability. Upon metal coordination, the assemblies exhibit pronounced crystallinity and exceptional thermal stability, as evidenced by persistent Bragg reflections and invariant d-spacings. Intriguingly, L2 : Fe (2 : 1) and L1 : L2 : Fe (0.5 : 0.5 : 1) in acetonitrile-d₃ (ACN-d₃) deviate from this trend, forming thermally labile amorphous gels. These systems show a complete loss of crystalline order, reduced Porod exponents—indicative of collapsed or branched fiber morphologies—and prominent melting and glass transition events in DSC. Fitting SANS and SAXS data to the correlation length model unveiled insightful nanostructural features. While most systems displayed minimal temperature-induced variation in mesh size or surface morphology, L2 : Ag in dimethyl sulfoxide-d₆ (DMSO-d₆)/D₂O and L2 : Fe (1 : 1) in ACN-d₃ exhibited a rare combination of thermally stable correlation lengths and increasing high-q exponents—strongly suggesting progressive fiber densification or surface smoothing within a robust gel framework. These findings highlight the tunability and structural resilience of supramolecular gels through precise control of ligand architecture, metal coordination, and temperature, offering valuable design principles for functional soft materials.