Catalysis enabled synthesis, structures, and reactivities of fluorinated S-corona[]arenes ( = 8-12).

Previously inaccessible large S-corona[]arene macrocycles ( = 8-12) with alternating aryl and 1,4-CF subunits are easily prepared on up to gram scales, without the need for chromatography (up to 45% yield, 10 different examples) through new high acceleration SAr substitution protocols (catalytic NRF in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NRF catalysis allows facile late-stage SAr difunctionalisation of the ring CF units with thiols (8 derivatives, typically 95+% yields) providing two-step access to highly functionalised fluoromacrocycle libraries. Macrocycle host binding supports fluoroaryl catalytic activation through contact ion pair binding of NRF and solvent inclusion. In the solid-state, solvent inclusion also intimately controls macrocycle conformation and fluorine-fluorine interactions leading to spontaneous self-assembly into infinite columns with honeycomb-like lattices.