MCD spectroscopy and TD-DFT calculations of a naphthalene-ring-bridged coplanar binuclear phthalocyanine dimer
- 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.
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- Date Issued: 2013
Synthesis and photophysical properties of covalent conjugates of aqua platinum (II) and octacarboxy-substituted zinc phthalocyanine
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
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- Date Issued: 2012
Trends in the optical and redox properties of tetraphenyltetraphenanthroporphyrins
- Authors: Mack, John , Lobb, Kevin , Nyokong, Tebello , Shen, Zhen , Kobayashi, Nagao
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245809 , vital:51407 , xlink:href="https://doi.org/10.1142/S1088424612500885"
- Description: The results of TD-DFT calculations for a series of tetraaryltetraphenanthroporphyrins containing para-substituents with differing electron donating and accepting properties are compared to the observed optical and redox properties and Michl's perimeter model is used as a conceptual framework for analyzing the results.
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- Date Issued: 2012
Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
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- Date Issued: 2009