Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency
Facile Two-Step Synthesis of 1,10-Phenanthroline-Derived Polyaza[7]helicenes with High Fluorescence and CPL Efficiency
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DOI：
10.1002/anie.201700507
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发表时间：
2017-03-27
影响因子：
16.6
通讯作者：
Shibata, Takanori
中科院分区：
文献类型：
--
作者：
Otani, Takashi;Tsuyuki, Ami;Shibata, Takanori
以2，9-二氯-1，10-菲咯啉为原料，通过与苯胺衍生物的双胺化反应和高价碘试剂介导的分子内双NH/CH偶联反应，两步合成了具有6-5-6- 6 -6-5-6骨架的氮杂[7]螺烯。螺旋烯的单晶X射线分析揭示了独特的结构，包括一个显着扭曲的中心和平面终端的骨架。氮杂螺烯在中性（Phi：0.25-0.55）和酸性（Phi：高达0.80）条件下均显示出高荧光量子产率（Fs）。对映体纯的氮杂[7]螺烯在中性和酸性条件下均显示出高的圆偏振发光（CPL）活性（g（lum）：高达0.009）。
A facile two-step synthesis of aza[7]helicenes possessing a 6-5-6-6-6-5-6 skeleton from commercially available 2,9-dichloro-1,10-phenanthroline via double amination with aniline derivatives followed by hypervalent iodine reagent-mediated intramolecular double-NH/CH couplings was developed. Single-crystal X-ray analyses of the helicenes revealed unique structures, including both a significantly twisted center and planar terminals of the skeleton. The azahelicenes show high fluorescent quantum yields (Fs) under both neutral (Phi: 0.25-0.55) and acidic conditions (Phi: up to 0.80). An enantiomerically pure aza[7] helicene showed high circularly polarized luminescence (CPL) activity under both neutral and acidic conditions (g(lum): up to 0.009).