Stoichiometric Control of Guest Recognition of Self-Assembled Palladium(II)-Based Supramolecular Architectures

We report flexible [Pd(L)2]2+ complexes where there is self-recognition, driven by & pi;-& pi; interactions between electron-rich aromatic arms and the cationic regions they are tethered to. This self-recognition hampers the association of these molecules with aromatic molecular targets in solution. In one case, this complex can be reversibly converted to an 'open' [Pd2(L)2]4+ macrocycle through introduction of more metal ion. This is accomplished by the ligand having two bidentate binding sites: a 2-pyridyl-1,2,3-triazole site, and a bis-1,2,3-triazole site. Due to favourable hydrogen bonding, the 2-pyridyl-1,2,3-triazole units reliably coordinate in the [Pd(L)2]2+ complex to control speciation: a second equivalent of Pd(II) is required to enforce coordination to bis-triazole sites and form the macrocycle. The macrocycle interacts with a molecular substrate with higher affinity. In this fashion we are able to use stoichiometry to reversibly switch between two different species and regulate guest binding. Stoichiometry can be used in a flexible system to switch between a 2+2 [Pd2(L)2]4+ macrocycle and a [Pd(L)2]2+ compound where the uncomplexed arms occlude access to the cationic part of the molecule by guests. We can thereby controllably regulate affinity between our host and an aromatic guest.image