Anion binding properties of a hollow PdL-cage

The hollow [PdL][BArF]2 complex 1 of a tetra-pyridyl (py) ligand (L) has a [Pd(py)4]2+ coordination environment. Addition of coordinating anions resulted in the formation of a neutral species with Pd(py)2(anion)2 coordination environment (12A). These species bind further to the coordinating anions in the order Cl- > N3- > Br- > I- > AcO- with Ka1 : 1 ≤ 414 M-1. With relatively non-coordinating anions 1 remains intact and displays 1 : 2 binding behaviour dominated by the 1 : 1 stoichiometry in the order NO3- (∼105 M-1) » ClO4- and BF4- (∼103 M-1). As evidenced by crystal structure data, DFT calculations and {1H-19F}-HOESY NMR with BF4-, the anions are bound by charge assisted [C-H]+···anion interactions.