Polyfluoroalkyl Chain-Based Assemblies for Biomimetic Catalysis

Amphiphobic fluoroalkyl chains are exploited for creating robust and diverse self-assembled biomimetic catalysts. Long terminal perfluoroalkyl chains (C_n F_2n+1 with n=6, 8, and 10) linked with a short perhydroalkyl chains (C_m H_2m with m=2 and 3) were used to synthesize several 1,4,7-triazacyclononane (TACN) derivatives, C_n F_2n+1 -C_m H_2m -TACN. In the presence of an equimolar amount of Zn²⁺ ions that coordinate the TACN moiety and drive the self-assembly into micelle-like aggregates, the critical aggregation concentration of polyfluorinated C_n F_2n+1 -C_m H_2m -TACN⋅Zn²⁺ was lowered by ∼1 order of magnitude compared to the traditional perhyroalkyl counterpart with identical carbon number of alkyl chain. When 2'-hydroxypropyl-4-nitrophenyl phosphate was used as the model phosphate substrate, polyfluorinated C_n F_2n+1 -C_m H_2m -TACN⋅Zn²⁺ assemblies showed higher affinity and catalytic activity, compared to its perhyroalkyl chain-based counterpart. Coarse-grained molecular dynamic simulations have been introduced to explore the supramolecular assembly of polyfluoroalkyl chains in the presence of Zn²⁺ ions and to better understand their enhanced catalytic activity.