Synthesis of nonaphenylenes and dodecaphenylenes using electron-transfer oxidation of Lipshutz cuprates and formation of nanostructural materials from hexadodecyloxynonaphenylene.

[摘要]：22, 75 Nonaphenylenes and dodecaphenylenes have been synthesized by using electron-transfer oxidn. of Lipshutz cuprates with duroquinone. Oxidn. of the Lipshutz cuprate derived from 4,4''-dibromo-o-terphenyl in THF produced nonaphenylene, whereas the similar oxidn. of the Lipshutz cuprates derived from 4,4''-diiodo-4',5'-dialkyl-o-terphenyls in ether afforded the corresponding nonaphenylenes and dodecaphenylenes in moderate total yields. In the case of 4,4''-diiodo-4',5'-didodecyloxy-o-terphenyl as the starting material, oxidn. of the corresponding Lipshutz cuprate in ether or THF only led to the formation of I (R = C12H25). Both the nonaphenylenes and dodecaphenylenes are unreactive to light, atm. oxygen, and prolonged heating. These oligophenylenes showed strong UV absorption and fluorescent emission and exhibited some redox properties on CV anal. Moreover, hexadodecyloxynonaphenylene I exhibits different nanostructures on the surface and in soln. to form a film by casting a soln. of I in cyclohexane, benzene, chloroform, THF, or diisopropyl ether (IPE) and nanofibers from IPE-MeOH (1:1), indicating different absorption and emission spectra and XRD patterns. The absorption maxima of THF soln., fiber, and film are in the order of I film (315 nm) > fiber (302 nm) > soln. (295 nm), whereas the emission maxima are in the order of I fiber (425 m) > soln. (418 nm) > film (401 nm). XRD anal. revealed that I aligns laterally on a glass or silicon surface to form a thin film with a lamella structure; however, it forms a nanofiber with a Lego-like stacking structure without p-p stacking interaction of the arom. rings. Reflecting the different nanostructures of the I film and fiber, a spin-coated I film is found to be effective in detecting the vapor of explosives due to the intercalation of nitroaroms. to the cracked surface of the loosely stacked I. In contrast, the I fiber is not effective in detection of nitroaroms. but exhibits fluorescence anisotropy. The max. fluorescence intensity is obtained in a direction perpendicular to the longitudinal axis of the fiber, indicating the stacking direction to be parallel to the longitudinal axis of the fiber.

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