@article { , title = {Catalysis enabled synthesis, structures, and reactivities of fluorinated S8-corona[n]arenes (n = 8–12)}, abstract = {Previously inaccessible large S8-corona[n]arene macrocycles (n = 8-12) with alternating aryl and 1,4-C6F4 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 SNAr substitution protocols (catalytic NR4F in pyridine, R = H, Me, Bu). Macrocycle size and functionality are tunable by precursor and catalyst selection. Equivalent simple NR4F catalysis allows facile late-stage SNAr difunctionalisation of the ring C6F4 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 NR4F 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.}, doi = {10.1039/d2sc05348a}, eissn = {2041-6539}, issn = {2041-6520}, issue = {1}, journal = {Chemical Science}, pages = {70-77}, publicationstatus = {Published}, publisher = {Royal Society of Chemistry (RSC)}, url = {https://nottingham-repository.worktribe.com/output/14602518}, volume = {14}, year = {2023}, author = {Turley, Andrew T. and Hanson-Heine, Magnus W. D. and Argent, Stephen P. and Hu, Yaoyang and Jones, Thomas A. and Fay, Michael and Woodward, Simon} }