Hierarchical self-assembly of fluorinated poly-N-heterocyclic carbene pillarplexes with anions

The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable. Here, we report a fluorinated N -heterocyclic carbene (NHC)–based pillarplex with a tunable quaternary structure, employed as an efficient building block for constructing hierarchical superstructures. Initially, multiple noncovalent interactions in the NHC-based pillarplex, particularly those between the fluorinated pillarplex and PF 6 - anions, induce the formation of a supramolecular gel at high concentrations. Additionally, this hierarchical self-assembled structure can be regulated by adjusting anion types, facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions. The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes. The hierarchical self-assembly of fluorinated pillarplex was tailored by various hierarchy levels and the appropriate steric preferences of the anion. The structural configurations and hierarchical self-assembly behaviors could impact the supramolecular arrangement, inner cavity and gelation property of the complex.