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An Air-Stable Organoboron Compound, Dithienooxadiborepine: Preparation and Functionalization

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journal contribution
posted on 22.06.2018, 00:00 authored by Qifan Yan, Mengxuan Yin, Cheng Chen, Yuankun Zhang
π-Conjugated organoboron molecules, which are easy to prepare, stable against moisture, and easy to functionalize, are scarce. Here, we report a one-pot synthesis of an air-stable organoboron compound, dithienooxadiborepine 1 in 17% yield on a 600 mg scale without separation or handling an air-sensitive intermediate. Dithienooxadiborepine 1 showed excellent stability under ambient conditions, allowing conventional column chromatography purification. Functionalization of 1 was realized via direct bromination using NBS and further Stille coupling reactions, giving access to longer π-conjugated molecules 5A and 5B. Single-crystal structures of compounds 4, 5A, and 5B not only unambiguously verified the chemical identity of dithienooxadiborepine 1 but also revealed that both the seven-member oxadiborepine ring and the 5–7–5 fused dithienooxadiborepine ring system are planar. UV–vis absorption and fluorescence emission measurements of 5A and 5B showed bathochromic shifted absorption and emission relative to 1, evidencing good π-conjugation. Cyclic voltammograms of 5A and 5B displayed two reduction peaks corresponding to two electron-accepting events at two boron atoms. These results proved dithienooxadiborepine 1 a potent π-conjugating building block for electron-accepting materials.