Dynamic Open Coordination Cage from Nonsymmetrical Imidazole-Pyridine Ditopic Ligands for Turn-On/Off Anion Binding

This work demonstrates a new nonconventional ligand design, imidazole/pyridine-based nonsymmetrical ditopic ligands (1 and 1^S ), to construct a dynamic open coordination cage from nonsymmetrical building blocks. Upon complex formation with Pd²⁺ at a 1:4 molar ratio, 1 and 1^S initially form mononuclear PdL₄ complexes (Pd²⁺ (1)₄ and Pd²⁺ (1^S )₄ ) without formation of a cage. The PdL₄ complexes undergo a stoichiometrically controlled structural transition to Pd₂ L₄ open cages ((Pd²⁺ )₂ (1)₄ and (Pd²⁺ )₂ (1^S )₄ ) capable of anion binding, leading to turn-on anion binding. The structural transitions between the Pd₂ L₄ open cage and the PdL₄ complex are reversible. Thus, stoichiometric addition (2 equiv) of free 1^S to the (Pd²⁺ )₂ (1^S )₄ open cage holding a guest anion ((Pd²⁺ )₂ (1^S )₄ ⋅G^- ) enables the structural transition to the Pd²⁺ (1^S )₄ complex, which does not have a cage and thus causes the release of the guest anion (Pd²⁺ (1^S )₄ +G^- ).