Terminal halogen-containing rod-like liquid crystals: Synthesis, self-assembly, photophysical and mechanochromism properties

Five series of cyanostilbene-based rod-like liquid crystals containing one different terminal atom (H, F, Cl, Br and I) at one end and one terminal aliphatic chain with different numbers of carbon atoms at the other end were reported by Suzuki coupling and Knoevenagel reactions. The influence of terminal halogen atoms and terminal chain length on the self-assembly, AIE behavior, temperature-dependent emission and mechanochromism behavior was explored by POM, DSC, XRD, SEM, absorption spectra and emission spectra. All the compounds are enantiotropic liquid crystals. The lowest non-halogen substituted homologue exhibited solo N phase, but the higher non-halogen substituted homologues exhibited mesogenic transition from SmA phase to N phase upon rising temperature. All the lowest halogen substituted homologues exhibited mesogenic transition from SmA phase to N phase upon rising temperature and all the higher homologues only exhibited SmA. The distinct mesogenic phase transition could be attributed to the intermolecular interaction produced by terminal halogen and the rigidity of the terminal aliphatic chain. All the non-halogen substituted compounds and halogen substituted compounds with smaller terminal halogen atom (F, Cl and Br atom) exhibited AIE behaviors, whereas the iodinated compounds exhibited extremely weak emission in solution and aggregated states due to the heavy atoms effect. These compounds also exhibited distinct solid-state emission with blue or cyan fluorescence, which could be quenched by increasing temperature. The reversible mechanochromism behavior was also achieved in all the compounds. The mechanical force induced quench in emission in non-halogen substituted compounds and halogen substituted compounds with smaller terminal halogen atom (F, Cl and Br atom), whereas enhancement in iodinated compounds. The reversible mechanochromism behavior endowed these compounds with potential applications in rewritable paper and anti-counterfeiting. The interesting properties in these liquid crystals would be attributed to the balance of the halogen-halogen interactions, heavy atom effect, steric-hindrance effect and chain length. These investigations would be helpful to understand the relationship between chemical structures and properties.