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A Chiral Hemiporphyrazine Derivative: Synthesis and Chiroptical Properties
Author(s) -
Wu Yanping,
Gai Lizhi,
Xiao Xuqiong,
Lu Hua,
Li Zhifang,
Mack John,
Harris Jessica,
Nyokong Tebello,
Shen Zhen
Publication year - 2016
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201600754
Subject(s) - circular dichroism , moiety , cyclic voltammetry , chemistry , wavelength , crystallography , spectral line , electron , atomic electron transition , stereochemistry , molecular physics , materials science , physics , electrochemistry , optoelectronics , electrode , quantum mechanics , astronomy
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.