Morphological Control of Heteroleptic <i>cis</i>‐ and <i>trans</i>‐Pd₂L₂L′₂ Cages

Abstract

Control over the integrative self-sorting of metallo-supramolecular assemblies opens up possibilities for introducing increased complexity and function into a single self-assembled architecture. Herein, the relationship between the geometry of three ligand components and morphology of three self-sorted heteroleptic [Pd₂ L₂ L'₂ ]⁴⁺ cages is examined. Pd-mediated assembly of two bis-monodentate pyridyl ligands with native bite angles of 75° and 120° affords a cis-[Pd₂ L₂ L'₂ ]⁴⁺ cage while the same reaction with two ligands with bite angles of 75° and 60° gives an unprecedented, self-penetrating structural motif; a trans-[Pd₂ (anti-L)₂ L'₂ ]⁴⁺ heteroleptic cage with a "doubly bridged figure eight" topology. Each heteroleptic assembly can be formed by cage-to-cage conversion of the homoleptic precursors and morphological control of [Pd₂ L₂ L'₂ ] cages is achieved by selective ligand displacement transformations in a system of three ligands and at least six possible cage products.