Inhibition of Ligand Binding Ability of Three Porphyrins by an Organic Effector.

A stimulus-responsive receptor 1 was designed and prepared to control the ligand-binding ability of three active sites, two zinc tetraphenylporphyrin units (P1) and one zinc diethynyldiphenylporphyrin unit (P2), with one effector molecule 2 . Bulky hexarylbenzene units are incorporated as shielding panels in the middle of the flexible side arms of 1 . Spectroscopic titrations indicated that a stable supramolecular complex 1 • 2 ( K 1 • 2 = 6.7 × 10 6 M -1 ) was produced via the cooperative formation of multiple hydrogen and coordination bonds. As the result, the binding of a ligand to P1 was inhibited by 2 in a competitive manner. Additionally, the formation of 1 • 2 brought about conformational restriction of the side arms to cover both faces of P2 with the shielding panels. The binding constant of 4-phenylpyridine with P2 in 1 • 2 decreased to 8.9% of that in 1 . Namely, the ligand-binding ability of P2 was inhibited according to an allosteric mechanism.

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