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In this work, we introduce a roll-to-roll system that can continuously print three-dimensional (3D) periodic nanostructures over large areas. This approach is based on Langmuir-Blodgett assembly of colloidal nanospheres, which diffract normal incident light to create a complex intensity pattern for near-field nanolithography. The geometry of the 3D nanostructure is defined by the Talbot effect and can be precisely designed by tuning the ratio of the nanosphere diameter to the exposure wavelength. Using this system, we have demonstrated patterning of 3D photonic crystals with a 500 nm period on a 50 × 200 mm2flexible substrate, with a system throughput of 3 mm/s. The patterning yield is quantitatively analyzed by an automated electron beam inspection method, demonstrating long-term repeatability of an up to 88% yield over a 4-month period. The inspection method can also be employed to examine pattern uniformity, achieving an average yield of up to 78.6% over full substrate areas. The proposed patterning method is highly versatile and scalable as a nanomanufacturing platform and can find application in nanophotonics, nanoarchitected materials, and multifunctional nanostructures.
Dearomative cycloaddition reactions represent an ideal means of converting flat arenes into three-dimensional architectures of increasing interest in medicinal chemistry. Quinolines, isoquinolines, and quinazolines, despite containing latent diene and alkene subunits, are scarcely applied in cycloaddition reactions because of the inherent low reactivity of aromatic systems and selectivity challenges. Here, we disclose an energy transfer–mediated, highly regio- and diastereoselective intermolecular [4 + 2] dearomative cycloaddition reaction of these bicyclic azaarenes with a plethora of electronically diverse alkenes. This approach bypasses the general reactivity and selectivity issues, thereby providing various bridged polycycles that previously have been inaccessible or required elaborate synthetic efforts. Computational studies with density functional theory elucidate the mechanism and origins of the observed regio- and diastereoselectivities.