A chiral hemiporphyrazine derivative
- Wu, Yanping, Gai, Lizhi, Xiao, Xuqiong, Lu, Hua, Li, Zhifang, Mack, John, Harris, Jessica, Nyokong, Tebello, Shen, Zhen
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: 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.
- Full Text:
- Date Issued: 2016
- Authors: Wu, Yanping , Gai, Lizhi , Xiao, Xuqiong , Lu, Hua , Li, Zhifang , Mack, John , Harris, Jessica , Nyokong, Tebello , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240404 , vital:50831 , xlink:href="https://doi.org/10.1002/asia.201600754"
- Description: 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.
- Full Text:
- Date Issued: 2016
Spectroscopic investigations and theoretical calculations of DABCO induced xanthene bridged self-assembled zinc (II) porphyrin dimer
- Xu, Li, Huang, Tingting, Liang, Xu, Mack, John, Harris, Jessica, Nyokong, Tebello, Li, Minzhi, Zhu, Weihua
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
- Full Text:
- Date Issued: 2016
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
- Full Text:
- Date Issued: 2016
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