Cooperative Loading and Release Behavior of a Metal–Organic Receptor

In order to design artificial chemical systems that are capable of achieving complex functions, it is useful to design synthetic receptors that mimic their biological counterparts. Biological functions are underpinned by properties that include specific binding with high affinity and selectivity, cooperativity, and release triggered by external stimuli. Here we show that a metal–organic receptor constructed through subcomponent self-assembly can selectively and cooperatively load and release oxocarbon anions. The flexible coordination spheres of its cadmium­(II) centers allow the receptor to dynamically adjust its structure upon exchanging four triflate or triflimide counterions for two oxocarbon anions, resulting in strong cooperativity and very tight binding, with an apparent association constant for C5O52– of 5 × 1010 M–1. Substituting the cadmium­(II) ions for copper­(I) by switching solvent prompted a structural reorganization and release of the oxocarbon anions. Its cooperative behavior allows the receptor to carry a greater payload than would be possible in a noncooperative analogue.