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

The design of structurally defined heteroleptic coordination cages is a challenging task, and only few examples are known to date. Here we describe selection approach that allowed the identification novel hexanuclear Pd cage containing two types dipyridyl ligands. A virtual combinatorial library [PdnL2n](BF4)2n complexes was prepared by mixing six different ligands with substoichiometric amounts [Pd(CH3CN)4](BF4)2. Analysis equilibrated reaction mixture revealed preferential formation [Pd6L6L'6](BF4)12 assembly. complex on preparative scale targeted synthesis, its structure elucidated single-crystal X-ray diffraction. It features an unprecedented trigonal-antiprismatic triangular Pd3L3 macrocycles bridged L' related but significantly larger obtained using metalloligands instead organic