Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Martynov, Alexander G, Mack, John, Ngoy, Bokolombe P, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
Photophysical and optical limiting properties of a novel distyryl-BODIPY with fused crown ether moieties
- May, Aviwe K, Stone, Justin, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello, Kimura, Mutsumi, Kobayashi, Nagao
- Authors: May, Aviwe K , Stone, Justin , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello , Kimura, Mutsumi , Kobayashi, Nagao
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239621 , vital:50749 , xlink:href="https://doi.org/10.1142/S1088424617500869"
- Description: The synthesis and characterization of a crown-ether-substituted 3,5-distyrylBODIPY dye with a 4-dimethylaminophenyl group at the meso-position is reported. The optical limiting properties were investigated at 532 nm, and the dye was found to have enhanced reverse saturable absorption responses during z-scan measurements. Theoretical calculations suggest that this may be due to the large dipole moment that is introduced by the benzo-fused crown ether and 4-dimethylaminophenyl substituents.
- Full Text:
- Date Issued: 2017
- Authors: May, Aviwe K , Stone, Justin , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello , Kimura, Mutsumi , Kobayashi, Nagao
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239621 , vital:50749 , xlink:href="https://doi.org/10.1142/S1088424617500869"
- Description: The synthesis and characterization of a crown-ether-substituted 3,5-distyrylBODIPY dye with a 4-dimethylaminophenyl group at the meso-position is reported. The optical limiting properties were investigated at 532 nm, and the dye was found to have enhanced reverse saturable absorption responses during z-scan measurements. Theoretical calculations suggest that this may be due to the large dipole moment that is introduced by the benzo-fused crown ether and 4-dimethylaminophenyl substituents.
- Full Text:
- Date Issued: 2017
Photophysical studies of meso-tetrakis (4-nitrophenyl) and meso-tetrakis (4-sulfophenyl) gallium porphyrins loaded into Pluronic F127 polymeric micelles
- Managa, Muthumuni, Ngoy, Bokolombe P, Mafukidze, Donovan M, Britton, Jonathan, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Mafukidze, Donovan M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233132 , vital:50060 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.08.033"
- Description: 5,10,15,20-Tetra(4-nitrophenyl) porphyrinato gallium chloride (ClGaTNPP) and 5,10,15,20-tetra(4-sulfophenyl) porphyrinato gallium chloride (ClGaTSPP) and their metal free derivatives were successfully synthesised and were added to Pluronic F127 polymeric micelles to form ClGaTNPP-F127 (or H2TNPP-F127) and ClGaTSPP-F127 (or H2TSPP-F127), respectively. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence lifetimes were short-lived upon incorporation into the polymer, compared to the porphyrin alone; suggesting the quenching of the lifetimes of the porphyrin by the polymers. Singlet oxygen quantum yields were determined to be 0.55 and 0.59 for ClGaTSPP and ClGaTSPP-F127, respectively. Thus there is an increase in singlet oxygen quantum yields in the presence of Pluronic F127 compared to the porphyrin alone. ClGaTSPP-F127 (or H2TSPP-F127) showed higher values of the binding constant (Kb) as well as high values of the Stern-Volmer constant (Ksv) compared to ClGaTNPP-F127 (or H2TNPP-F127).
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Mafukidze, Donovan M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233132 , vital:50060 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.08.033"
- Description: 5,10,15,20-Tetra(4-nitrophenyl) porphyrinato gallium chloride (ClGaTNPP) and 5,10,15,20-tetra(4-sulfophenyl) porphyrinato gallium chloride (ClGaTSPP) and their metal free derivatives were successfully synthesised and were added to Pluronic F127 polymeric micelles to form ClGaTNPP-F127 (or H2TNPP-F127) and ClGaTSPP-F127 (or H2TSPP-F127), respectively. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence lifetimes were short-lived upon incorporation into the polymer, compared to the porphyrin alone; suggesting the quenching of the lifetimes of the porphyrin by the polymers. Singlet oxygen quantum yields were determined to be 0.55 and 0.59 for ClGaTSPP and ClGaTSPP-F127, respectively. Thus there is an increase in singlet oxygen quantum yields in the presence of Pluronic F127 compared to the porphyrin alone. ClGaTSPP-F127 (or H2TSPP-F127) showed higher values of the binding constant (Kb) as well as high values of the Stern-Volmer constant (Ksv) compared to ClGaTNPP-F127 (or H2TNPP-F127).
- Full Text:
- Date Issued: 2017
The photophysical studies of Pluronic F127/P123 micelle mixture system loaded with metal free and Zn 5, 10, 15, 20-tetrakis [4-(benzyloxy) phenyl] porphyrins
- Managa, Muthumuni, Ngoy, Bokolombe P, Nyokong, Tebello
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
- Authors: Managa, Muthumuni , Ngoy, Bokolombe P , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188932 , vital:44799 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.02.018"
- Description: Binary mixtures of Pluronics are studied as drug nanocarriers in this work. H2 and Zn 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin were encapsulated onto binary micelle mixture of Pluronic F127/P123. The fluorescence and singlet oxygen generating behaviour of the porphyrins were investigated following incorporation. The fluorescence quantum yield for H2TBnOPP (ΦF = 0.034) was higher than that of ZnTBnOPP (ΦF = 0.023) and decreased when ZnTBnOPP or H2TBnOPP when in the presence of Pluronic F127/P123 binary mixtures. The kq values were 2.8 × 108 and 3.7 × 108 M−1 s−1, for H2TBnOPP + Pluronic F127/P123 and ZnTBnOPP + Pluronic F127/P123 in water, respectively. The binding constants (Kb) were 1.58 × 105 M−1 and 1.02 × 105 M−1 for ZnTBnOPP + Pluronic F127/P123 and H2TBnOPP + Pluronic F127/P123, respectively.
- Full Text:
- Date Issued: 2017
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