An orientational change from homeotropic to planar of liquid crystal (LC) mesogens and the microphase separation (MPS) domains is attained by the segregated skin layer at the free surface. This allows for an efficient in-plane photoalignment of the cylindrical domains. The surface segregation strategy is very simple and is therefore expected to open up new possibilities for the orientation control of various types of LC materials.

Borylzincate was generated in situ from dialkylzinc, diboron, and metal alkoxide. Model DFT calculations showed that although the formation of borylzincate is kinetically favorable, it is thermodynamically unfavorable. Therefore, we designed a successive reaction sequence that would provide a compensating energy gain. This enabled Zn-catalyzed borylation of aryl halides and borylzincation of benzynes and terminal alkyne from diborons without the need for any cocatalyst.

Laminated bilayer films comprised of photoresponsive azobenzene-containing liquid crystalline polymer skin layers adhered on a thick elastomeric substrate were prepared, and the wrinkle formation upon uniaxial compression was investigated. Irradiation with UV light at 365 nm led to the disappearance of the wrinkle or reduction of wrinkle wavelength, depending on the content of azobenzene unit in the polymer. Such photoresponsive modulations of wrinkle formation could be well correlated with the photoinduced changes in the Young’s modulus determined by indentation–retraction force curve measurements using an AFM cantilever. Additionally, the thickness modulation of the skin layer caused by the photoinduced mass migration can also be applied to modify the wrinkle wavelength. These photoresponsive surface wrinkle modulations are anticipated to offer new possibilities for the surface microfabrication technology.

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We present the first trans-selective diborylation reaction of alkynes. By means of theoretical calculation-assisted reaction analysis, we designed a pseudo-intramolecular reaction of diboron, propargyl alcohol, and a base to facilitate B-B bond activation and C-B bond formation with high efficiency. This approach provides synthetically versatile and densely functionalized 4-borylated 1,2-oxaborol-2(5H)-oles (vinyldiboronates) in a straightforward manner. Detailed computational analysis showed that the directing alkoxide functionality markedly lowers the activation energy of B-C bond formation.