A Catalogue of Orthogonal Complementary Ligand Pairings for Palladium(II) Complexes

Molecular recognition is a form of information transfer, seen in the base pairing in DNA which is derived from the identity (acceptor or donor) and number of hydrogen bond sites within each base. Here we report bis-ligand palladium(II) complexes that exhibit similar complementarity. Pd(II) has square planar four-coordinate geometry, giving control over ligand orientation and denticity. Pairings were developed using ligand denticity (3 : 1 or 2 : 2), and hydrogen bond capability (AA:DD or AD:DA) or lack thereof. Five pairings were investigated, with two sets of four being found fully orthogonal. The two 3 : 1 pairings exhibited limited ligand exchange. The extent of this exchange varied dependant on solvent from 2 : 1 (desired to undesired) to 6 : 1. A reliable and varied set of ligand pairs have therefore been developed for bis-ligand coordination sphere engineering in pursuit of sorting for complex molecular architectures and molecular-level information storage and transfer events.