Flexibility and Dynamicity Enhances and Controls Supramolecular Self‐Assembly of Zinc(II) Metallogels

Abstract Supramolecular self‐assembly of stacked architectures is typically achieved through hydrogen bonding or π–π interactions between monomers constructed from stable and inert bonds. In contrast, coordinative interactions of early metals promise distinct self‐assembly behaviour due to more flexible bonding geometries and a wider range of stabilities and exchange kinetics. In this report we demonstrate that tailoring the flexible coordination sphere of Zinc(II) complexes via subtle ligand modification promotes not only one but also three‐dimensional self‐assembly both thermodynamically and kinetically into higher‐order fibrous morphologies, the latter being elucidated by electron tomography. As a result, coordination chemistry can be translated into both nanoscopic (fibre stiffness) and macroscopic (thermal gel stability) material properties. Utilizing dynamicity enables gelation via subcomponent self‐assembly, constructing the supramolecular polymer network simultaneously with the monomer. Furthermore, coordinative dis‐ and reassembly via metal‐ligand exchange reactions involving the first and second coordination spheres allows for control over gelation and emission of the system. Our report links concepts in supramolecular self‐assembly and coordination chemistry by leveraging the unique bonding interactions that cannot be achieved for traditional monomers, promising applications in stimuli‐responsive optoelectronics.