Unveiling the Role of Hydrogen Bonds in Luminescent N-Annulated Perylene Liquid Crystals.

We report the liquid-crystalline (LC) and luminescent properties of a series of N-annulated perylenes (1-4) in whose molecular structures amide and ester groups alternate. We found that the LC properties of these compounds not only depend on the number of hydrogen-bonding units, but also on the relative position of the amide linkers in the molecule. The absence of amide groups in compound 1 leads to no LC properties, whereas four amide groups induce the formation of a wide temperature range columnar hexagonal phase in compound 4. Remarkably, compound 3, with two amide groups in the inner part of the structure, stabilizes the columnar LC phases better than its structural isomer 2, with the amide groups in the outer part of the molecule. Similarly, we found that only compounds 1 and 2, which have no hydrogen bonding units in the inner part of the molecule, exhibit luminescence vapochromism upon exposure to organic solvent vapors.