Allosteric regulation of supramolecular oligomerization and catalytic activity via coordination-based control of competitive hydrogen-bonding events

Herein, we demonstrate that the activity of a hydrogen-bond-donating (HBD) catalyst embedded within a coordination framework can be allosterically regulated in situ by controlling oligomerization via simple changes in coordination chemistry at distal Pt(II) nodes. Using the halide-induced ligand rearrangement reaction (HILR), a heteroligated Pt(II) triple-decker complex, which contains a catalytically active diphenylene squaramide moiety and two hydrogen-bond-accepting (HBA) ester moieties, was synthesized. The HBD and HBA moieties were functionalized with hemilabile ligands of differing chelating strengths, allowing one to assemble them around Pt(II) nodes in a heteroligated fashion. Due to the hemilabile nature of the ligands, the resulting complex can be interconverted between a flexible, semiopen state and a rigid, fully closed state in situ and reversibly. FT-IR spectroscopy, ¹H DOSY, and ¹H NMR spectroscopy titration studies were used to demonstrate that, in the semiopen state, intermolecular hydrogen-bonding between the HBD and HBA moieties drives oligomerization of the complex and prevents substrate recognition by the catalyst. In the rigid, fully closed state, these interactions are prevented by steric and geometric constraints. Thus, the diphenylene squaramide moiety is able to catalyze a Friedel-Crafts reaction in the fully closed state, while the semiopen state shows no reactivity. This work demonstrates that controlling catalytic activity by regulating aggregation through supramolecular conformational changes, a common approach in Nature, can be applied to man-made catalytic frameworks that are relevant to materials synthesis, as well as the detection and amplification of small molecules.