Tuning the Size and Geometry of Heteroleptic Coordination Cages by Varying the Ligand Bent Angle

Spherical assemblies of the type [Pd_n L_2n ]²ⁿ⁺ can be obtained from Pd^II salts and curved N-donor ligands, L. It is well established that the bent angle, α, of the ligand is a decisive factor in the self-assembly process, with larger angles leading to complexes with a higher nuclearity, n. Herein, we report heteroleptic coordination cages of the type [Pd_n L_n L'_n ]²ⁿ⁺ , for which a similar correlation between the ligand bent angle and the nuclearity is observed. Tetranuclear cages were obtained by combining [Pd(CH₃ CN)₄ ](BF₄ )₂ with 1,3-di(pyridin-3-yl)benzene and ligands featuring a bent angle of α=120°. The use of a dipyridyl ligand with α=149° led to the formation of a hexanuclear complex with a trigonal prismatic geometry; for linear ligands, octanuclear assemblies of the type [Pd₈ L₈ L'₈ ]¹⁶⁺ were obtained. The predictable formation of heteroleptic Pd^II cages from 1,3-di(pyridin-3-yl)benzene and different dipyridyl ligands is evidence that there are entire classes of heteroleptic cage structures that are privileged from a thermodynamic point of view.