Solvent-Induced Self-Assembly of PdL and PdL Coordination Cages for Benzene-Cyclohexane Separation.

We report the solvato-controlled synthesis of novel PdL-based bowl-shaped cages, specifically tetrafacial ( = 4) and trifacial ( = 3), constructed using -blocked 90° Pd(II) acceptors and a planar tetratopic ligand. The reaction of the ligand with (tmeda)Pd(ONO) in water produced a trifacial cage (), which quickly converted into a tetrafacial cage () in dimethyl sulfoxide (DMSO). Alternatively, the self-assembly of the ligand with (en)Pd(ONO) in water yielded an equilibrium mixture of tetrafacial () and trifacial () cages that exhibited reversible structural transformations in response to solvent changes.