Donor-Site-Directed Rational Assembly of Heteroleptic cis-[Pd2 L2 L'2 ] Coordination Cages from Picolyl Ligands.

A donor-site engineering approach facilitates the formation of heteroleptic [Pd2 L2 L'2 ]4+ cage structures through a favored cis-'in2 /out2 ' spatial configuration of the methyl groups of 5- and 3-substituted bis-monodentate picolyl ligands with flat acridone and bent phenothiazine backbones. The heteroleptic cages were confirmed by ESI-MS and 2D NMR experiments as well as DFT calculations, which pointed toward a cis-configuration being energetically favored. This was further supported by the synthesis and X-ray structure of a previously unreported cis-[Pd(2-picoline)4 ]2+ complex. The formation of homoleptic structures, however, was met with considerable steric hindrance at the PdII centers, as observed by the formation of [Pd2 L3 (solvent)2 ]4+ and [Pd2 L2 (solvent)4 ]4+ species when only one type of acridone-based ligand was offered. In contrast, bent phenothiazine ligands with outside-pointing methyl groups showed the ability to form interpenetrated double-cages, as revealed by X-ray crystallography. The general route presented herein enables the assembly of uniform cis-[Pd2 L2 L'2 ]4+ coordination cages, thus furthering the possibility to increase structural and functional complexity in supramolecular systems.