Controlling the Complexity and Interconversion Mechanisms in Self-Assembled [Fe₂ L₃ ]⁴⁺ Helicates and [Fe₄ L₆ ]⁸⁺...

Self-assembled coordination cages and metal-organic frameworks have relied extensively on symmetric ligands in their formation. Here we have prepared a relatively simple system employing an unsymmetric ligand that results in two distinct self-assembled structures, a [Fe₂ L₃ ]⁴⁺ helicate and a [Fe₄ L₆ ]⁸⁺ cage composed of 10 interconverting diastereomers and their enantiomers. We show that the steric profile of the ligand controls the complexity, thermodynamics and kinetics of interconversion of the system.