Anomalous Chiral Transfer: Supramolecular Polymerization in a Chiral Medium of a Mesogenic Molecule
Anomalous Chiral Transfer: Supramolecular Polymerization in a Chiral Medium of a Mesogenic Molecule
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反常手性转移：介晶分子手性介质中的超分子聚合
DOI：
10.1002/asia.202200223
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Aida Takuzo
中科院分区：
文献类型：
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作者：
Zhang Xu‐Jie;Morishita Daiki;Aoki Tsubasa;Itoh Yoshimitsu;Yano Keiichi;Araoka Fumito;Aida Takuzo
在这里，我们报告了在5-氰基联苯CB * 的手性介质中，基于四苯基卟啉的非手性氢键单体（TPP）的超分子聚合中的介质到聚合物的异常手性转移。TPP在（R）-CB*（[TPP]=7.7 mol %）中的混合物在40 °C下得到柱状倾斜LC中间相，其中各个柱由TPP的光学活性螺旋超分子聚合物组成，这是成功的介质到聚合物手性转移的结果。 同时，当用非手性5-氰基联苯CB稀释CB * 时，体系的旋光性与CB */CB的组成呈异常的钟形关系，在CB */CB=50/50时的gabs值为0.049，是单独CB * 的gabs值的6.0倍。 这种异常的手旋光放大在CD是最有可能的，由于在倾斜的柱状LC在横向压缩时的TPP的堆叠几何形状的变化。
Here, we report a medium‐to‐polymer anomalous chiral transfer in the supramolecular polymerization of a tetraphenylporphyrin‐based achiral hydrogen‐bonding monomer (TPP) in a chiral medium of 5‐cyanobiphenylCB*. A mixture ofTPPin (R)‐CB*([TPP]=7.7 mol %) at 40 °C gave a columnar oblique LC mesophase, where the individual columns were composed of an optically active helical supramolecular polymer ofTPPas a consequence of a successful medium‐to‐polymer chiral transfer. Meanwhile, upon dilution ofCB*with achiral 5‐cyanobiphenylCB, the optical activity of the system showed an anomalous bell‐shaped dependency on the composition ofCB*/CB, where thegabsvalue of 0.049 atCB*/CB=50/50 was 6.0 times larger than thegabsvalue ofCB*alone. Such anomalous chiroptical amplification in CD is most likely due to a change in the stacking geometry ofTPPin the oblique columnar LC upon lateral compression.