Friš?i?, T.Elacqua, E.Dutta, S.Oburn, S.M.MacGillivray, L.R.2026-02-052020Crystal Growth and Design, 2020, 20, 4, pp. 2584-258915287483https://doi.org/10.1021/acs.cgd.9b01712https://idr.nitk.ac.in/handle/123456789/23967A series of templated solid-state reactions are used to construct the â&tild;bent' isomer of the [2.2]cyclophane family of molecules. Small-molecule hydrogen-bond-donor templates based on resorcinol complete the supramolecular construction of ortho-, meta-, and para-[2.2]cyclophanes in the solid state. The family of exo,exo-dicyclobutyl[2.2]cyclophanes forms regiospecifically in up to quantitative yields. The confines of the organic solid state and the modular nature of the template approach allow for the generation of a less stable exo,endo-[2.2]metacyclophane by simply changing the template to enforce a concomitant change in self-assembly. Our results demonstrate the first completed solid-state construction of each member of the family of [2.2]cyclophanes. © © 2020 American Chemical Society.Hydrogen bondsMoleculesSupramolecular chemistryHydrogen bond donorsModular controlQuantitative yieldsSmall moleculesSolid-state constructionTemplate approachTotal synthesis[2.2]cyclophanesSolid state reactions