Fabrication and manipulation of macroscopically ordered nanostructures in polymer films via supramolecular selforganization 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.

Hierarchically arranged stripes of photoswitchable liquid crystal polymers (LCPs) containing azobenzene moieties were conveniently crafted via a flow-enabled self-assembly (FESA). Interestingly, by subjecting a drop of LCP solution to dry in a restricted geometry comprising two nearly parallel plates with a stationary upper plate and a movable lower plate that programmably traveled in a "stop-and-move" manner during the FESA process, photoswitchable LCP stripes were yielded, displaying two modes of deposition, namely, periodic primary stripes of large dimensions and regularly spaced secondary stripes of small dimensions situated between adjacent primary stripes (i.e., forming hierarchical LCP stripes). Notably, these hierarchical azobenzene moieties-containing stripes demonstrated sequential photoinduced reversible phase transition (i.e., photoswitching) due to the thickness difference between primary and secondary stripes. A UV light-induced expansion effect was observed on the LCP stripes. Clearly, such rapid creation of hierarchical stripes by FESA represents a robust means of organizing polymers, nanoparticles, colloids, DNA, etc. into complex yet ordered patterns over a large area in a simple and controllable manner for potential use in surface relief grating, photoactuators, photoswitchable devices, antifake labels, etc.

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