Reversible Restrain and Release of the Dynamic Valence Isomerization in a Shape-shifting Bullvalene by Complex...

In search for structural features that enable the control of the valence isomerization of the fluxional bullvalene, a bullvalene-bis(harmane) conjugate is identified that acts as chelating ligand in complexes with metal ions. Spectrometric titrations show that this ligand forms 1 : 1 complexes with Ag⁺, Cu⁺, Cu²⁺, and Zn²⁺. Most importantly, detailed NMR-spectroscopic analysis at different temperatures reveals that the complexation with Ag⁺ strongly affects the dynamic isomerization of the bullvalene unit of the ligand such that only one predominant valence isomer is formed, even at 5 °C. Detailed ¹H-NMR-spectroscopic studies disclose an increased barrier (~11 kJ mol^-1) of the Cope rearrangement. Furthermore, the addition of hexacyclene displaces the Ag⁺ from the complex, so that the valence isomerization is accelerated and an equilibrium with two predominant isomers is formed. In turn, repeated addition of Ag⁺ regains the complex with the restrained isomerization of the bullvalene unit. This method to control the valence isomerism by straightforward chemical stimuli may be used to simplify structural analysis at elevated temperatures, i. e. a feature not available so far with bullvalenes, and it may be employed as functional element in dynamic supramolecular assemblies.