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Previously inaccessible large S 8 -corona[ n ]arene macrocycles ( n = 8-12) with alternating aryl and 1,4-C 6 F 4 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 S N Ar substitution protocols (catalytic NR 4 F in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NR 4 F catalysis allows facile late-stage S N Ar difunctionalisation of the ring C 6 F 4 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 NR 4 F 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., Competing Interests: The macrocycle 1a is now commercially available from https://www.keyorganics.net, A. T. T and S. W. declare their interest in this venture., (This journal is © The Royal Society of Chemistry.)