Enhanced Ordering and Efficient Photoalignment of Nanostructures in Block Copolymers Enabled by Halogen Bond

Fabrication and manipulation of macroscopically ordered nanostructures in polymer films via supramolecular self-organization are fascinating from the viewpoints of science and technology. Here, a halogen bond (XB) was introduced into a block copolymer to facilitate its microphase separation process upon XB-driven supramolecular self-assembly. To the best of our knowledge, this is an extremely rare example to elegantly maneuver nanostructures of polymers by the emerging supramolecular interaction, XB. The nonmesogenic block copolymer composed of poly(ethylene oxide) and azopyridine-containing polymethacrylate was transformed into a supramolecular liquid-crystalline polymer through the halogen-bonded interaction between 1,2-diiodo-3,4,5,6-tetrafluorobenzene and the azopyridine group with the optimal molar ratio of 1:1. For comparison, one hydrogen-bonded liquid-crystalline polymer was also fabricated but no such ordering enhancement was acquired, indicating that both the high directionality of XB and the resulting supramolecular mesogenic ordering played key roles in the enhanced ordering of nanostructures in polymer films. In addition, efficient photoalignment and photoreorientation of nanostructures coinciding with the oriented direction of the supramolecular mesogens were also obtained by manipulating photoirradiation of linearly polarized light for the present XB-involved liquid-crystalline block copolymer, which is promising for the development of a novel generation of advanced composite liquid crystal (LC) materials.