<p>In this study, the synthesis, structural characterisation and mesomorphic and optical properties of seven new bent-shaped and polycatenar bent-shaped compounds derived from chalcone and cyanopyridine are reported. The mesomorphic behaviour was investigated by differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction (XRD) and correlated with the molecular structure. Two bent-core hexacatenars molecules (Ic and IIc) presented liquid crystalline properties, showing a hexagonal columnar (Col<sub>h</sub>) phases at room temperature, being each disc constituted by two mesogens. Optical studies were also performed for the final molecules, being conducted by ultraviolet-visible and fluorescence spectrometry. The cyanopyridine derivatives show moderate luminescence quantum yields, ranging between 18% and 27%, with emission maxima around 371 nm. It is also shown that while the chalcone central unit favours a calamitic liquid crystalline behaviour in molecules with lower number of aliphatic chains, a polycatenar structure with cyanopyridine as the central unit favours a Col<sub>h</sub> arrangement, also providing luminescence properties to the molecule.</p
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