Macrocyclic and Lantern Complexes of Palladium(II) with Bis(amidopyridine) Ligands: Synthesis, Structure, and Host−Guest Chemistry

The reactions of [PdCl2(NCPh)2] in a 1:1 ratio with the bis(amidopyridine) ligands LL = C6H3(5-R)(1,3-CONH-3-C5H4N)2 with R = H (1a) or R = t-Bu (1b) give the corresponding neutral dipalladium(II) macrocycles trans,trans-[Pd2Cl4(μ-LL)2], 2a and 2b, which crystallize from dimethylformamide with one or two solvent molecules as macrocycle
guests. The reaction of [PdCl2(NCPh)2] with LL in a 1:2 ratio gave the cationic lantern complex [Pd2(μ-LL)4]Cl4, 3c
(LL = 1b), and the reaction in the presence of AgO2CCF3 gave the corresponding trifluoroacetate salts [Pd2(μ-LL)4](CF3CO2)4, 3a (LL = 1a) and 3b (LL = 1b). These lantern complexes exhibit a remarkable host−guest chemistry,
as they can encapsulate cations, anions, and water molecules by interaction of the guest with either the electrophilic
NH or the nucleophilic CO substituents of the amide groups, which can be directed toward the center of the
lantern through easy conformational change. The structures of several of these host−guest complexes were
determined, and it was found that the cavity size and shape vary according to the ligand conformation, with Pd···Pd separations in the range from 9.45 to 11.95 Å. Supramolecular ordering of the lanterns was observed in the
solid state, through either hydrogen bonding or secondary bonding to the cationic palladium(II) centers. The selective
inclusion by the lantern complexes of alkali metal ions in the sequence Na+ ≫ K+ ≫ Li+ was observed by ESI-MS.