Identification of a Heteroleptic Pd₆L₆L′₆ Coordination Cage by Screening of a Virtual Combinatorial Library

Abstract

The design of structurally defined heteroleptic coordination cages is a challenging task, and only few examples are known to date. Here we describe a selection approach that allowed the identification of a novel hexanuclear Pd cage containing two types of dipyridyl ligands. A virtual combinatorial library of [Pd_<i>n</i>L_2<i>n</i>](BF₄)_2<i>n</i> complexes was prepared by mixing six different dipyridyl ligands with substoichiometric amounts of [Pd(CH₃CN)₄](BF₄)₂. Analysis of the equilibrated reaction mixture revealed the preferential formation of a heteroleptic [Pd₆L₆L'₆](BF₄)₁₂ assembly. The complex was prepared on a preparative scale by a targeted synthesis, and its structure was elucidated by single-crystal X-ray diffraction. It features an unprecedented trigonal-antiprismatic cage structure with two triangular Pd₃L₃ macrocycles bridged by six L' ligands. A related but significantly larger [Pd₆L₆L'₆](BF₄)₁₂ cage was obtained by using metalloligands instead of organic dipyridyl ligands.