A Chiral Hemiporphyrazine Derivative: Synthesis and Chiroptical Properties.
A Chiral Hemiporphyrazine Derivative: Synthesis and Chiroptical Properties.
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手性半紫菜嗪衍生物：合成和手性光学性质。
DOI：
10.1002/asia.201600754
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Zhen Shen
中科院分区：
文献类型：
--
作者：
Yanping Wu;Lizhi Gai;Xuqiong Xiao;Hua Lu;Zhifang Li;J. Mack;Jessica Harris;T. Nyokong;Zhen Shen
报道了具有手性联萘取代基的光学活性半卟啉的合成，提供了将本征手性部分引入半卟啉类似物的大环核心的第一个实例。在（S，S）-1的CD光谱的325-450 nm区域观察到负的圆二色性（CD）信号，而在220-325 nm区域观察到主要的正带。 在（R，R）-1和（S，S）-1的CD光谱的整个波长范围内观察到镜像对称性。用循环伏安法观察到起始电位为1.07 V的不可逆单电子氧化波和沿着的-0.85V的可逆单电子还原波。 密度泛函计算再现实验观察到的数据和趋势，并提供进一步的洞察电子跃迁的性质。
The synthesis of an optically active hemiporphyrazine with chiral binaphthyl substituents (1) is reported, providing the first example of the incorporation of an intrinsically chiral moiety into the macrocyclic core of a hemiporphyrazine analogue. A negative circular dichroism (CD) signal is observed in the 325-450 nm region of the CD spectrum of (S,S)-1, while mainly positive bands are observed in the 220-325 nm region. Mirror symmetry is observed across the entire wavelength range of the CD spectra of (R,R)-1 and (S,S)-1. An irreversible one-electron oxidation wave with an onset potential at 1.07 V is observed by cyclic voltammetry, along with a reversible one-electron reduction wave at -0.85 V. Density functional calculations reproduce the experimentally observed data and trends, and provide further insight into the nature of the electronic transitions.