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A liquid crystalline homopolymer that has photoisomerizable methoxyazobenzene groups in the side chain has been synthesized and characterized. Thin films of the nematic glassy phase of this polymer have been processed in order to study the absorption spectra and the vibrational and electronic circular dichroism responses by irradiation with 488 nm circularly polarized light (CPL). Selective reflection of visible light demonstrates that the irradiation of this glassy nematic azopolymer induces a helix as a consequence of the chiral arrangement of the azobenzene units. Moreover, a wedge cell with an aligning layer for planar orientation was filled with the polymer with the aim of investigating the change in the macroscopic optical properties and optical textures of the azopolymer on irradiation with CPL. The transfer of chirality from CPL to azopolymer through chiral conformations is proposed as a model for explaining the supramolecular chirality.

Iodoalkynes [1,benzene (p-BIB) and 1,3-bis(iodoethynyl)benzene (m-BIB)] have been used successfully to prepare halogen bonding complexes with a range of 4-pyridine derivatives showing liquid crystalline organizations. The trimeric halogen-bonded complexes obtained from p-BIB have a rod-like structure and exhibited high order calamitic phases (SmB and G). In contrast, m-BIB gives rise to bent-shaped structures that display SmAP-like mesophases. Furthermore it was found that the presence of three and five aromatic rings in these halogen-bonding complexes promotes calamitic mesophases while seven rings are required to stabilize bent-core mesophases. The formation of halogen bonding in the complexes was confirmed by several techniques, including FT-IR, XPS, and single crystal X-ray diffraction and the strength of the bonds was evaluated by DFT calculations

A series of liquid crystalline homopolymers that have photoisomerizable cyanoazobenzene groups in the side chain has been synthesized and characterized. Thin films of these polymers have been processed in order to study the absorption spectra and circular dichroism responses after illumination with 488 nm circularly polarized light. The tendency of the azobenzene units to aggregate and the modification of the electronic spectra by illumination were studied by UV-vis spectroscopy. Illumination with circularly polarized light of the azopolymers gave rise to a photoinduced circular dichroism response, which suggests supramolecular structures with a chiral orientation of the azobenzene chromophores in H-aggregates. The photoinduced supramolecular order depends on the polymer structure, i.e., on the T g and the length of the flexible spacer, and the nature of the liquid crystal phase. Identical absorption spectra and reverse circular dichroism spectra were obtained after irradiation with circularly polarized light of opposite handedness and this is due to the photoinduction of enantiomeric supramolecular structures. The thermal stability above T g of the photoinduced supramolecular chirality is determined by the polymer structure.

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