Spontaneous Multi-scale Supramolecular Assembly Driven by Noncovalent Interactions Coupled with the Continuous...

Reported herein is the multi-scale supramolecular assembly (MSSA) process along with redox reactions driven by supramolecular interactions coupled with the spontaneous Marangoni effect in ionic liquid (IL)-based extraction systems. The black powder, the single sphere with a black exterior, and the single colorless sphere were formed step by step at the interface when an aqueous solution of KMnO₄ was mixed with the IL phase 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (C₂OHmimNTf₂) bearing octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO). The mechanism of the whole process was studied systematically. The phenomena were related closely to the change in the valence state of Mn. The MnO₄^- ion could be reduced quickly to δ-MnO₂ and further to Mn²⁺ slowly by the hydroxyl-functionalized IL C₂OHmimNTf₂. Based on Mn²⁺, Mn(CMPO)₃²⁺, elementary building blocks (EBBs), and [EBB] clusters were generated step by step. The [EBB] clusters with the large enough size that were transferred to the interface, together with the remaining δ-MnO₂, assembled into the single sphere with a black exterior, driven by supramolecular interactions coupled with the spontaneous Marangoni effect. When the remaining δ-MnO₂ was used up, the mixed single sphere turned completely colorless. It was found that the reaction site of C₂OHmim⁺ with Mn(VII) and Mn(IV) was distributed mainly at the side chain with a hydroxyl group. The MSSA process presents unique spontaneous phase changes. This work paves the way for the practical application of the MSSA-based separation method developed recently. The process also provides a convenient way to observe in situ and characterize directly the continuous Marangoni effect.