Embedding of Functionalized Coordination Cages and a Molecular Knot in a Polymeric Membrane for Potentiometric Sensing of Environmentally Important Oxyanions and Halides.

Three kinds of coordination cages and a molecular knot with inductively activated P-H, N-H, or C-H hydrogen bond donors anchoring in the functionalized cavities were inspected as ionophores to develop polymeric membrane ISEs for potentiometric sensing of environmentally important oxyanions and halides. The proposed ISEs displayed significant preference for perrhenate, phosphate, or chloride with a selectivity pattern distinctively different from the sequence depending on the Gibbs free energy of hydration owing to the high degree of shape, charge, and size selectivity originating from the rigidity and complementarity of the binding cavities. To gain further insight into the response characters of the proposed ISEs, the binding constants of ionophore-anion complexes in the membrane phase were investigated, and the binding affinity, together with the Hofmeister series, correlates well with the determined selectivity pattern of the proposed ISEs. Optimizing the composition of the membrane such as lipophilic additives and plasticizers produced ISEs displaying Nernstian/near-Nernstian potentiometric responses to primary anions with a wide linear range, improved detection limits, good reversibility, and satisfying lifetime. Potentiometric determination of perrhenate, phosphate, and chloride in river water, mineral water, and artificial serum samples was achieved with good recovery and accuracy using the proposed ISEs, demonstrating their potential for real-life applications. These results will shed new light on how novel ionophores could be designed for potentiometric sensing and broaden the scope of host-guest chemistry of coordination cages and molecular knots.