Wide-Gap 1D-, 2D-, and 3D-Hydrogen-Bonded Organic Frameworks Hierarchically Weaved by Macrocyclic Supramolecular Multifluorine Tectons

A series of 1D-, 2D-, and 3D-hydrogen-bonded organic frameworks (1D-, 2D-, and 3D-HOFs) force-driven by macrocyclic multifluorine tectons (F-tectons) was constructed on the basis of burgeoning multifluorinated diaminoterephthalates (25, 345, and 26). Crystalline 25 gave ladder-shaped 1D-HOFs containing one kind of macrocyclic F-tecton looped by two F···H(CH3) hydrogen bonds in competition with strong π···πand π···H(CH3) interactions. Crystalline 345 gave layer-by-layer translational 2D-HOFs containing hierarchically macrocyclic F-tectons looped by 8-fold hydrogen bonds, including three F···H(CH3), three =O···HN and two ArC···H(CH3) prior to weak π···πinteractions. Crystalline 26 possessed 2-fold interpenetrated 3D-HOFs containing hierarchically macrocyclic F-tectons looped by F···H(CH3), ArH···F, and ArH···F···H(CH3) hydrogen bonds and interpenatrated by strong π···πinteractions. In addition to that, the electron-withdrawing multifluorination of diaminoterephthalates caused an optical blue shift with wide optical energy gaps (2.43-2.51 eV) for 25, 345, and 26 in solution and a wide optical band gap (2.31 eV) for 345 in the film state. The multifluorination effect confirms an interesting trend that more F atoms bring in deeper highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) energy levels (345 vs 25/26) and also regioisomerism confirms that farther F atoms bring in deeper HOMO/LUMO energy levels (25 vs 26).