Synthesis, photophysical and photochemical studies on long chain zinc phthalocyanine derivatives
- Ogunsipe, Abimbola, Durmus, Mahmut, Atilla, Devrim, Gürek, Ayşe Gül, Ahsen, Vefa, Nyokong, Tebello
- Authors: Ogunsipe, Abimbola , Durmus, Mahmut , Atilla, Devrim , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/266019 , vital:53910 , xlink:href="https://doi.org/10.1016/j.synthmet.2008.06.007"
- Description: The synthesis and characterization of 2,9,16,23-chloro-3,10,17,24-triethyleneoxysulphanylphthalocyaninato zinc(II) (CTESZnPc) is described. The photophysics and photochemistry of CTESZnPc and those of tetrakis(triethyleneoxysulphanyl)zinc phthalocyanine (TTESZnPc) and octakis(triethyleneoxysulphanyl)zinc phthalocyanine (OTESZnPc), are presented and compared with those of unsubstituted zinc phthalocyanine (ZnPc). The presence of triethyleneoxysulphanyl substituents on the ZnPc ring gave rise to higher values of singlet oxygen (ΦΔ) and photodegradation (ΦPd) quantum yields in DMF. However, TTESZnPc, OTESZnPc and CTESZnPc are less fluorescent than ZnPc, judging from their fluorescence quantum yield (ΦF) values. Fluorescence was lower in toluene than in DMF due to aggregation in the former solvent. Triplet quantum yield (ΦT) values were found to increase with the presence of substituents on the ZnPc ring, while triplet lifetimes (τT) were found to vary linearly with the logarithms of solvent viscosities. The fluorescences of the substituted ZnPc complexes were effectively quenched by benzoquinone (BQ), and the quenching data analyzed by the Stern–Volmer equation. The Stern–Volmer constants and the diffusion-controlled bimolecular rate constants were calculated.
- Full Text:
- Date Issued: 2008
- Authors: Ogunsipe, Abimbola , Durmus, Mahmut , Atilla, Devrim , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/266019 , vital:53910 , xlink:href="https://doi.org/10.1016/j.synthmet.2008.06.007"
- Description: The synthesis and characterization of 2,9,16,23-chloro-3,10,17,24-triethyleneoxysulphanylphthalocyaninato zinc(II) (CTESZnPc) is described. The photophysics and photochemistry of CTESZnPc and those of tetrakis(triethyleneoxysulphanyl)zinc phthalocyanine (TTESZnPc) and octakis(triethyleneoxysulphanyl)zinc phthalocyanine (OTESZnPc), are presented and compared with those of unsubstituted zinc phthalocyanine (ZnPc). The presence of triethyleneoxysulphanyl substituents on the ZnPc ring gave rise to higher values of singlet oxygen (ΦΔ) and photodegradation (ΦPd) quantum yields in DMF. However, TTESZnPc, OTESZnPc and CTESZnPc are less fluorescent than ZnPc, judging from their fluorescence quantum yield (ΦF) values. Fluorescence was lower in toluene than in DMF due to aggregation in the former solvent. Triplet quantum yield (ΦT) values were found to increase with the presence of substituents on the ZnPc ring, while triplet lifetimes (τT) were found to vary linearly with the logarithms of solvent viscosities. The fluorescences of the substituted ZnPc complexes were effectively quenched by benzoquinone (BQ), and the quenching data analyzed by the Stern–Volmer equation. The Stern–Volmer constants and the diffusion-controlled bimolecular rate constants were calculated.
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- Date Issued: 2008
The photophysical studies of a mixture of CdTe quantum dots and negatively charged zinc phthalocyanines
- Moeno, Sharon, Nyokong, Tebello
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268663 , vital:54220 , xlink:href="https://doi.org/10.1016/j.poly.2008.03.007"
- Description: Fluorescence resonance energy transfer (FRET) studies were carried out with quantum dots capped with thioglycolic acid (TGA) and 2-mercaptoethanol (2-ME) and negatively charged phthalocyanines {Zn tetracarboxy (ZnTCPc), Zn octacarboxy (ZnOCPc) and Zn tetrasulfo (ZnTSPc) phthalocyinines} in a 0.1 NaOH:EtOH (50:50) solvent mixture. The best overlap between emission spectra of the donor (QDs) and the absorption spectra of the acceptor (ZnPc derivatives) was observed for TGA capped QDs, very little overlap was obtained for 2-ME QDs. ZnTSPc gave the highest FRET efficiency (0.3), with ZnOCPc and ZnTCPc giving a FRET efficiency of 0.2. The ΦT values of the MPcs generally decreased in the presence of the QD whereas the triplet lifetimes (τT) of the ZnPc derivatives were higher in the presence of QDs.
- Full Text:
- Date Issued: 2008
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268663 , vital:54220 , xlink:href="https://doi.org/10.1016/j.poly.2008.03.007"
- Description: Fluorescence resonance energy transfer (FRET) studies were carried out with quantum dots capped with thioglycolic acid (TGA) and 2-mercaptoethanol (2-ME) and negatively charged phthalocyanines {Zn tetracarboxy (ZnTCPc), Zn octacarboxy (ZnOCPc) and Zn tetrasulfo (ZnTSPc) phthalocyinines} in a 0.1 NaOH:EtOH (50:50) solvent mixture. The best overlap between emission spectra of the donor (QDs) and the absorption spectra of the acceptor (ZnPc derivatives) was observed for TGA capped QDs, very little overlap was obtained for 2-ME QDs. ZnTSPc gave the highest FRET efficiency (0.3), with ZnOCPc and ZnTCPc giving a FRET efficiency of 0.2. The ΦT values of the MPcs generally decreased in the presence of the QD whereas the triplet lifetimes (τT) of the ZnPc derivatives were higher in the presence of QDs.
- Full Text:
- Date Issued: 2008
The synthesis and electrochemical behaviour of water soluble manganese phthalocyanines: Anion radical versus Mn(I) species
- Sehlotho, Nthapo, Durmuş, M, Ahsen, N, Nyokong, Tebello
- Authors: Sehlotho, Nthapo , Durmuş, M , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
- Full Text:
- Date Issued: 2008
- Authors: Sehlotho, Nthapo , Durmuş, M , Ahsen, N , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6596 , http://hdl.handle.net/10962/d1004345
- Description: The following MnPc derivatives were synthesized: 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5a), quaternized 1,(4)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (5b), 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH) (6a) and quaternized 2,(3)-tetra-(2-mercaptopyridine) phthalocyaninato manganese(III)(OH)(6b). Spectro-electrochemistry shows that the reduction of Mn(II)Pc to Mn(I)Pc occurs only when the complexes are in their quaternized form (5b and 6b). The reduction (to Mn(I)Pc(−2)) of the quaternized form occurs at a lower potential than that (to Mn(II)Pc(−3)) of the unquaternized form. This observation suggests that metal reduction (to Mn(I)Pc(−2)) versus ligand reduction (to Mn(II)Pc(−3)) in Mn(II)Pc complexes depends on the nature of the ring substituents.
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- Date Issued: 2008
Tuning the redox properties of Co-N4 macrocyclic complexes for the catalytic electrooxidation of glucose
- Villagra, Evelyn, Bedioui, Fethi, Nyokong, Tebello, Canales, J Carlos, Sancy, Mamie, Páez, Maritza A, Costamagna, Juan, Zagal, Jose H
- Authors: Villagra, Evelyn , Bedioui, Fethi , Nyokong, Tebello , Canales, J Carlos , Sancy, Mamie , Páez, Maritza A , Costamagna, Juan , Zagal, Jose H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268675 , vital:54221 , xlink:href="https://doi.org/10.1016/j.electacta.2008.02.006"
- Description: Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes.
- Full Text:
- Date Issued: 2008
- Authors: Villagra, Evelyn , Bedioui, Fethi , Nyokong, Tebello , Canales, J Carlos , Sancy, Mamie , Páez, Maritza A , Costamagna, Juan , Zagal, Jose H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268675 , vital:54221 , xlink:href="https://doi.org/10.1016/j.electacta.2008.02.006"
- Description: Graphite electrodes modified with four different cobalt N4 macrocyclics, namely Co tetrapentapyridinophthalocyanine, (CoTPenPyrPc), Co tetrapyridinoporphyrazine (CoTPyPz), Co octa(hydroxyethylthio)phthalocyanine (CoOEHTPc) and Co tetranitrophthalocyanine (CoTNPc) exhibit catalytic activity for the oxidation of glucose in alkaline media. The purpose of this work is to establish correlations between the catalytic activity of these complexes and their redox potential. The activity of the different modified electrodes was tested by linear voltammetry under hydrodynamic conditions using the rotating disk technique. Tafel plots constructed from mass-transport corrected currents give slopes ranging from 0.080 to 0.160 V/decade for the different catalysts which suggests that a first one-electron step is rate controlling with the symmetry of the energy barrier depending on the nature of the ligand of the Co complex. A plot of log I versus the Co(II)/(I) formal potential gives a volcano curve that also includes catalysts studied previously. This illustrates the concept that the formal potential of the catalyst needs to be tuned to a certain value for achieving maximum activity. A theoretical interpretation of these results is given in terms of Langmuir isotherms for the adsorption of glucose on the Co sites of the surface-confined metal complexes.
- Full Text:
- Date Issued: 2008
Volcano correlations for the reactivity of surface-confined cobalt N4-macrocyclics for the electrocatalytic oxidation of 2-mercaptoacetate
- Claußen, Jan A, Ochoa, Gonzalo, Páez, Maritza, Costamagno, Juan, Gulppi, Miguel, Nyokong, Tebello, Bedioui, Fethi, Zagal, José H
- Authors: Claußen, Jan A , Ochoa, Gonzalo , Páez, Maritza , Costamagno, Juan , Gulppi, Miguel , Nyokong, Tebello , Bedioui, Fethi , Zagal, José H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268688 , vital:54222 , xlink:href="https://doi.org/10.1007/s10008-007-0336-y"
- Description: We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B12, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin larger than Co–tetrasulfonatotetraphenylporphyrin larger than Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B12 exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N4-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site.
- Full Text:
- Date Issued: 2008
- Authors: Claußen, Jan A , Ochoa, Gonzalo , Páez, Maritza , Costamagno, Juan , Gulppi, Miguel , Nyokong, Tebello , Bedioui, Fethi , Zagal, José H
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268688 , vital:54222 , xlink:href="https://doi.org/10.1007/s10008-007-0336-y"
- Description: We have investigated the electrocatalytic activity of several substituted and unsubstituted cobalt–phthalocyanines of substituted tetraphenyl porphyrins and of vitamin B12, for the electro-oxidation of 2-mercaptoacetate, with the complexes pre-adsorbed on a pyrolytic graphite electrode. Several N4-macrocyclic were used to have a wide variety of Co(II)/(I) formal potentials. The electrocatalytic activity, measured as current at constant potential, increases with the Co(II)/(I) redox potential for porphyrins as Co–pentafluorotetraphenylporphyrin larger than Co–tetrasulfonatotetraphenylporphyrin larger than Co-2,2′,2″,2‴tetra-aminotetraphenylporphyrin and decreases for cobalt phthalocyanines as Co-3,4-octaethylhexyloxyphthalocyanine > Co–octamethoxyphthalocyanine > Co–tetranitrophthalocyanine Co–tetraaminophthalocyanine > Co–unsubstituted phthalocyanine > Co–tetrasulfonatophthalocyanine > Co–perfluorinated phthalocyanine. Vitamin B12 exhibits the maximum activity. A correlation of log I (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. This clearly shows that the search for better catalysts for this reaction point to those N4-macrocyclic complexes with Co(II)/(I) formal potentials close to −0.84 V versus SCE, which correspond to an optimum situation for the interaction of the thiol with the active site.
- Full Text:
- Date Issued: 2008
City Press Rapport Prestige Award 2008
- Authors: Nyokong, Tebello
- Identifier: vital:7219 , http://hdl.handle.net/10962/d1005896
- Description: City Press/Rapport Prestige Award – in celebration of South Africa’s inspirational women achievers.
- Full Text: false
- Authors: Nyokong, Tebello
- Identifier: vital:7219 , http://hdl.handle.net/10962/d1005896
- Description: City Press/Rapport Prestige Award – in celebration of South Africa’s inspirational women achievers.
- Full Text: false