The Weak-Link Approach (WLA) to supramolecular chemistry uses coordination chemistry to design stimuli-responsive and switchable nanoscale architectures (e.g., molecular tweezers, macrocycles, tri-layer structures) that mimic allostery found in proteins. Herein, we expand the control over structure afforded by the WLA to another class of supramolecular materials and synthesize the first crystalline, WLA-based 1D coordination polymers (WLA-ICPs). The reaction of a closed, WLA monomer complex featuring pendant pyridine moieties with Cu(BF4)2●6H2O in acetonitrile or N,N-dimethylformamide yields three isostructural 1D zig-zag chains that were characterized via single-crystal X-ray diffraction. One of the coordination polymers was further investigated by nuclear magnetic resonance and mass spectrometry in the presence of a chemical effector (halide ion, Cl−). Importantly, these studies showed that the model WLA-ICP retains the structural switchability of the embedded WLA monomer complex. Upon exposure to Cl− anions, it disassembles into its molecular components, including the fully-opened congener of the initial WLA complex, demonstrating control over the macroscale chain assembly via the structural state of the nanoscale WLA monomer complex. Taken together, this work represents a promising method for the construction of allosteric, stimuli-responsive coordination polymers, including higher-ordered structures such as metal-organic frameworks.

Structurally dynamic crystalline 1D coordination polymers enabled via the weak-link approach

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