Oxidation of an Internal‐Edge‐Substituted [5]Helicene‐Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence
Oxidation of an Internal‐Edge‐Substituted [5]Helicene‐Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence
复制标题
内部边缘取代的[5]螺旋烯衍生的膦的氧化同步增强圆偏振发光
DOI：
10.1002/chem.202202922
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Karasawa Satoru
中科院分区：
文献类型：
--
作者：
Usui Kazuteru;Narita Nozomi;Eto Ryosuke;Suzuki Seika;Yokoo Atsushi;Yamamoto Kosuke;Igawa Kazunobu;Iizuka Naoko;Mimura Yuki;Umeno Tomohiro;Matsumoto Shota;Hasegawa Masashi;Tomooka Katsuhiko;Imai Yoshitane;Karasawa Satoru
具有圆二色性的手性有机小分子在电子学和生物学等领域有着广泛的应用前景，因而受到人们的广泛关注。在此，我们揭示了一个系统，其中的膦基基团的氧化为相应的氧化膦的螺烯衍生物的内缘诱导CPL响应。侧向π-延伸的7，8-二氢[5]螺旋烯，其内螺旋边缘上带有膦和氧化膦基团（即，C1位），并通过X射线晶体学明确确定其螺旋结构。这些化合物的物理（紫外/可见光和发射）和手性性质进行了研究，在各种溶剂中。尽管它们的结构相似，但氧化膦显示出比膦更好的CPL响应，具有高的发射不对称因子（|闷闷不乐|=（1.3-1.9）×10−3），这可以归因于螺旋烯螺旋内部的结构变化。
Small chiral organic molecules with CD properties are in high demanded due to their potential use in promising electronic and biological applications. Herein, we reveal a system in which the oxidation of a phosphino group to the corresponding phosphine oxide on the inner rim of a helicene derivative induces a CPL response. Laterally π‐extended 7,8‐dihydro[5]helicenes bearing phosphine and phosphine oxide groups on their inner helical rims (i. e., the C1 position) were synthesized, and their helical structures were unambiguously determined by X‐ray crystallography. The photophysical (UV/visible and emission) and chiroptical properties of these compounds were investigated in various solvents. Despite their structural similarities, phosphine oxide showed a significantly better CPL response than phosphine, with a high dissymmetry factor for emission (|glum|=(1.3–1.9)×10−3) that can be attributed to structural changes in the interior of the helicene helix.