Two macrocyclic tetralactam
receptors are shown to selectively
encapsulate anionic, square-planar chloride and bromide coordination
complexes of gold(III), platinum(II), and palladium(II). Both receptors
have a preorganized structure that is complementary to its precious
metal guest. The receptors do not directly ligate the guest metal
center but instead provide an array of arene π-electron donors
that interact with the electropositive metal and hydrogen-bond donors
that interact with the outer electronegative ligands. This unique
mode of supramolecular recognition is illustrated by six X-ray crystal
structures showing receptor encapsulation of AuCl<sub>4</sub><sup>–</sup>, AuBr<sub>4</sub><sup>–</sup>, PtCl<sub>4</sub><sup>–2</sup>, or Pd<sub>2</sub>Cl<sub>6</sub><sup>–2</sup>. In organic solution, the 1:1 association constants correlate with
specific supramolecular features identified in the solid state. Technical
applications using these receptors are envisioned in a wide range
of fields that involve precious metals, including mining, recycling,
catalysis, nanoscience, and medicine