A Chiral Hemiporphyrazine Derivative: Synthesis and Chiroptical Properties |
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| Authors: | Yanping Wu Lizhi Gai Dr Xuqiong Xiao Dr Hua Lu Zhifang Li Dr John Mack Jessica Harris Prof?Dr Tebello Nyokong Zhen Shen |
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| Institution: | 1. Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou, P. R. China;2. State Key Laboratory of Coordination Chemistry, Nanjing National Laboratoryof Microstructures, Nanjing University, Nanjing, P. R China;3. Department of Chemistry, Rhodes University, Grahamstown, South Africa |
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| Abstract: | 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. |
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| Keywords: | chirality circular dichroism computational chemistry hemiporphyrazine macrocycles |
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