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
MCD spectroscopy and TD-DFT calculations of a naphthalene-ring-bridged coplanar binuclear phthalocyanine dimer
- Mack, John, Liang, Xu, Dubinina, Tatiana V, Tomilova, Larisa G, Nyokong, Tebello, Kobayashi, Nagao
- Authors: Mack, John , Liang, Xu , Dubinina, Tatiana V , Tomilova, Larisa G , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232511 , vital:49998 , xlink:href="https://doi.org/10.1142/S1088424613500259"
- Description: Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations are used to analyze the electronic structure and optical properties of an alkyl-substituted naphthalene-ring-bridged coplanar binuclear phthalocyanine dimer. An analysis of the MCD spectrum of the naphthalene-ring-bridged dimer relative to those of benzene-bridged compounds reported previously, demonstrates that there is a significantly weaker interaction between the two phthalocyanine rings. TD-DFT results obtained using the B3LYP functional with 6–31G basis sets were found to be problematic. Closer agreement with the experimental data is obtained when the CAM-B3LYP functional is used instead. The naphthalene-ring-bridged compound is found to be unsuitable for use as a photosensitizer for the formation of singlet oxygen, because the ΦT values are negligible.
- Full Text:
- Date Issued: 2013
- Authors: Mack, John , Liang, Xu , Dubinina, Tatiana V , Tomilova, Larisa G , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/232511 , vital:49998 , xlink:href="https://doi.org/10.1142/S1088424613500259"
- Description: Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations are used to analyze the electronic structure and optical properties of an alkyl-substituted naphthalene-ring-bridged coplanar binuclear phthalocyanine dimer. An analysis of the MCD spectrum of the naphthalene-ring-bridged dimer relative to those of benzene-bridged compounds reported previously, demonstrates that there is a significantly weaker interaction between the two phthalocyanine rings. TD-DFT results obtained using the B3LYP functional with 6–31G basis sets were found to be problematic. Closer agreement with the experimental data is obtained when the CAM-B3LYP functional is used instead. The naphthalene-ring-bridged compound is found to be unsuitable for use as a photosensitizer for the formation of singlet oxygen, because the ΦT values are negligible.
- Full Text:
- Date Issued: 2013
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Liang, Xu, Xu, Li, Li, Minzhi, Mack, John, Stone, Justin, Nyokong, Tebello, Jiang, Yu, Kobayashi, Nagao, Zhu, Weihua
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Language: English
- Type: Article
- Identifier: vital:7292 , http://hdl.handle.net/10962/d1020355
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety. , Original publication is available at http://dx.doi.org/10.1142/S1088424615500492
- Full Text: false
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Language: English
- Type: Article
- Identifier: vital:7292 , http://hdl.handle.net/10962/d1020355
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety. , Original publication is available at http://dx.doi.org/10.1142/S1088424615500492
- Full Text: false
- «
- ‹
- 1
- ›
- »