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 center dot center dot center dot H(CH3) hydrogen bonds in competition with strong pi center dot center dot center dot pi, and pi center dot center dot center dot 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 center dot center dot center dot H(CH3), three =O center dot center dot center dot HN and two ArC center dot center dot center dot H(CH3) prior to weak pi center dot center dot center dot pi interactions. Crystalline 26 possessed 2-fold interpenetrated 3D-HOFs containing hierarchically macrocyclic F-tectons looped by F center dot center dot center dot H(CH3), ArH center dot center dot center dot F, and ArH center dot center dot center dot F center dot center dot center dot H(CH3) hydrogen bonds and interpenatrated by strong pi center dot center dot center dot pi interactions. 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 ).