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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  n  L 2 n  ](BF 4 ) 2 n  complexes was prepared by mixing six different dipyridyl ligands with substoichiometric amounts of [Pd(CH 3 CN) 4 ](BF 4 ) 2 . Analysis of the equilibrated reaction mixture revealed the preferential formation of a heteroleptic [Pd 6 L 6 L' 6 ](BF 4 ) 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 Pd 3 L 3 macrocycles bridged by six L' ligands. A related but significantly larger [Pd 6 L 6 L' 6 ](BF 4 ) 12 cage was obtained by using metalloligands instead of organic dipyridyl ligands.

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

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