Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293279 , vital:57071 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/293279 , vital:57071 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
- Full Text:
- Date Issued: 2007
Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283140 , vital:55914 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283140 , vital:55914 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.018"
- Description: The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical properties of aryloxy tetra-substituted gallium and indium phthalocyanine derivatives
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281431 , vital:55724 , xlink:href="https://doi.org/10.1016/j.tet.2006.11.089"
- Description: The synthesis, photophysical and photochemical properties of the tetra-substituted aryloxy gallium(III) and indium(III) phthalocyanines are reported for the first time. General trends are described for photodegradation, singlet oxygen, fluorescence, and triplet quantum yields and triplet lifetimes of these compounds. The introduction of phenoxy and tert-butylphenoxy substituents on the ring resulted in lowering of fluorescence quantum yields and lifetimes, and triplet quantum yields, and an increase of kIC, kISC, and kF. Photoreduction of the complexes was observed during laser flash photolysis. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.41 to 0.91. Thus, these complexes show potential as Type II photosensitizers.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281431 , vital:55724 , xlink:href="https://doi.org/10.1016/j.tet.2006.11.089"
- Description: The synthesis, photophysical and photochemical properties of the tetra-substituted aryloxy gallium(III) and indium(III) phthalocyanines are reported for the first time. General trends are described for photodegradation, singlet oxygen, fluorescence, and triplet quantum yields and triplet lifetimes of these compounds. The introduction of phenoxy and tert-butylphenoxy substituents on the ring resulted in lowering of fluorescence quantum yields and lifetimes, and triplet quantum yields, and an increase of kIC, kISC, and kF. Photoreduction of the complexes was observed during laser flash photolysis. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.41 to 0.91. Thus, these complexes show potential as Type II photosensitizers.
- Full Text:
- Date Issued: 2007
Synthesis, Photophysical and Photochemical Properties of Poly (oxyethylene)‐Substituted Phthalocyaninato Oxotitanium (IV) Complexes
- Atilla, Devrim, Durmus, Mahmut, Yılmaz, Özgür, Gürek, Ayşe Gül, Ahsen, Vefa, Nyokong, Tebello
- Authors: Atilla, Devrim , Durmus, Mahmut , Yılmaz, Özgür , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271263 , vital:54526 , xlink:href="https://doi.org/10.1002/ejic.200700057"
- Description: The synthesis, photophysical and photochemical properties of tetra- and chlorotetrapoly(oxyethylene)-substituted oxotitanium(IV) phthalocyanines are reported for the first time. The new compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. These complexes showed monomeric behaviour in solution. General trends are described for photodegredation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethyl sulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The complexes showed high triplet quantum yields and triplet lifetimes in DMSO. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism), were 0.72 and 0.78 for 3a and 5a, respectively. Thus, these complexes show potential as Type II photosensitizers. These complexes were also quenched by benzoquinone for fluorescence quenching studies.
- Full Text:
- Date Issued: 2007
- Authors: Atilla, Devrim , Durmus, Mahmut , Yılmaz, Özgür , Gürek, Ayşe Gül , Ahsen, Vefa , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271263 , vital:54526 , xlink:href="https://doi.org/10.1002/ejic.200700057"
- Description: The synthesis, photophysical and photochemical properties of tetra- and chlorotetrapoly(oxyethylene)-substituted oxotitanium(IV) phthalocyanines are reported for the first time. The new compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. These complexes showed monomeric behaviour in solution. General trends are described for photodegredation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethyl sulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The complexes showed high triplet quantum yields and triplet lifetimes in DMSO. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism), were 0.72 and 0.78 for 3a and 5a, respectively. Thus, these complexes show potential as Type II photosensitizers. These complexes were also quenched by benzoquinone for fluorescence quenching studies.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical properties of tetra-and octa-substituted gallium and indium phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271276 , vital:54529 , xlink:href="https://doi.org/10.1016/j.poly.2007.03.007"
- Description: The synthesis, photophysical and photochemical properties of the tetra- and octa-[4-(benzyloxyphenoxy)] substituted gallium(III) and indium(III) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. General trends are described for quantum yields of photodegredation, fluorescence quantum yields and lifetimes, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulfoxide (DMSO). Substituted indium phthalocyanine complexes (7b–9b) showed much higher quantum yields of triplet state and shorter triplet lifetimes, compared to the substituted GaPc derivatives due to enhanced intersystem crossing (ISC) in the former. The gallium and indium phthalocyanine complexes showed phototransformation during laser irradiation due to ring reduction. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.51 to 0.94. Thus, these complexes show potential as photodynamic therapy of cancer.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271276 , vital:54529 , xlink:href="https://doi.org/10.1016/j.poly.2007.03.007"
- Description: The synthesis, photophysical and photochemical properties of the tetra- and octa-[4-(benzyloxyphenoxy)] substituted gallium(III) and indium(III) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H NMR spectroscopy and electronic spectroscopy. General trends are described for quantum yields of photodegredation, fluorescence quantum yields and lifetimes, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulfoxide (DMSO). Substituted indium phthalocyanine complexes (7b–9b) showed much higher quantum yields of triplet state and shorter triplet lifetimes, compared to the substituted GaPc derivatives due to enhanced intersystem crossing (ISC) in the former. The gallium and indium phthalocyanine complexes showed phototransformation during laser irradiation due to ring reduction. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.51 to 0.94. Thus, these complexes show potential as photodynamic therapy of cancer.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical studies of new water-soluble indium (III) phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283976 , vital:56007 , xlink:href="https://doi.org/10.1039/b618478b"
- Description: The preparation of water-soluble indium(III)phthalocyanine complexes is described for the first time in this study. Peripherally and non-peripherally 3-hydroxypyridine tetrasubstituted indium(III) phthalocyanines (5a, 6a) and their quaternarized derivatives (5b, 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b, 6b) show excellent solubility in water, which makes them potential photosensitizers for use in photodynamic therapy (PDT) applications. Photochemical and photophysical measurements were conducted on 3-pyridyloxy appended indium(III) phthalocyanines in dimethylsulfoxide (DMSO) for non-ionic (5b, 6b) derivatives. General trends are described for quantum yields of photodegradation, fluorescence lifetimes, fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) are very high (ΦΔ > 0.55). Thus, these complexes may be useful as Type II photosensitizers.
- Full Text:
- Date Issued: 2007
Synthesis, photophysical and photochemical studies of new water-soluble indium (III) phthalocyanines
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283976 , vital:56007 , xlink:href="https://doi.org/10.1039/b618478b"
- Description: The preparation of water-soluble indium(III)phthalocyanine complexes is described for the first time in this study. Peripherally and non-peripherally 3-hydroxypyridine tetrasubstituted indium(III) phthalocyanines (5a, 6a) and their quaternarized derivatives (5b, 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b, 6b) show excellent solubility in water, which makes them potential photosensitizers for use in photodynamic therapy (PDT) applications. Photochemical and photophysical measurements were conducted on 3-pyridyloxy appended indium(III) phthalocyanines in dimethylsulfoxide (DMSO) for non-ionic (5b, 6b) derivatives. General trends are described for quantum yields of photodegradation, fluorescence lifetimes, fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) are very high (ΦΔ > 0.55). Thus, these complexes may be useful as Type II photosensitizers.
- Full Text:
- Date Issued: 2007
The effects of fire on post-fire seed germination of selected Savanna woody species
- Authors: Shackleton, Charlie M
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183104 , vital:43912 , xlink:href=" https://doi.org/10.1111/j.1365-2028.2007.00766.x"
- Description: Although fire is recognized as an integral component of savanna dynamics, there is a dearth of understanding of its impacts on woody plant seeds. This study examined the impacts of fire in stimulating or constraining post-fire germination of seven common savanna woody species. Seeds of two species (Combretum hereroense and Euclea natalensis) failed to germinate irrespective of fire treatment. For the remaining five species, fire effects were dependent on seed location as either on the soil surface or buried. For surface seeds, fire effects reduced germination in four of the species, and stimulated it for one species (Acacia swazica). For buried seeds, fire had no effect. A significant proportion of surface seeds were destroyed by fire, and overall germination was higher for buried seed for most species other than A. swazica.
- Full Text:
- Date Issued: 2007
- Authors: Shackleton, Charlie M
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/183104 , vital:43912 , xlink:href=" https://doi.org/10.1111/j.1365-2028.2007.00766.x"
- Description: Although fire is recognized as an integral component of savanna dynamics, there is a dearth of understanding of its impacts on woody plant seeds. This study examined the impacts of fire in stimulating or constraining post-fire germination of seven common savanna woody species. Seeds of two species (Combretum hereroense and Euclea natalensis) failed to germinate irrespective of fire treatment. For the remaining five species, fire effects were dependent on seed location as either on the soil surface or buried. For surface seeds, fire effects reduced germination in four of the species, and stimulated it for one species (Acacia swazica). For buried seeds, fire had no effect. A significant proportion of surface seeds were destroyed by fire, and overall germination was higher for buried seed for most species other than A. swazica.
- Full Text:
- Date Issued: 2007
The synthesis, fluorescence behaviour and singlet oxygen studies of new water-soluble cationic gallium (III) phthalocyanines
- Durmus, Mahmut, Nyokong, Tebello
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/280207 , vital:55586 , xlink:href="https://doi.org/10.1016/j.inoche.2006.11.012"
- Description: The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.
- Full Text:
- Date Issued: 2007
- Authors: Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/280207 , vital:55586 , xlink:href="https://doi.org/10.1016/j.inoche.2006.11.012"
- Description: The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.
- Full Text:
- Date Issued: 2007
Thiol oxidation at 2-mercaptopyrimidine-appended cobalt phthalocyanine modified glassy carbon electrodes
- Obirai, Joseph C, Nyokong, Tebello
- Authors: Obirai, Joseph C , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281403 , vital:55722 , xlink:href="https://doi.org/10.1016/j.jelechem.2006.10.033"
- Description: The electrocatalytic activity of cobalt tetra-2-mercaptopyrimidylphthalocyanine-modified glassy carbon electrode (CoTMPyrPc-GCE) toward gluthathione, L-cysteine and 2-mercaptoethanol has been investigated. CoTMPyrPc-GCE provides a significant improvement on the reported oxidation potential of L-cysteine in pH 4.0 phosphate buffered solution. The oxidation peak potential (Ep), for L-cysteine, was 0.15 V – a relatively lowered oxidation potential compared to reported phthalocyanine complexes. The electrode prepared by drop-dry/thermal annealing method was very stable and sensitive over a long period of time. The stability has been attributed to the thermal annealing and the structure of the mercaptopyrimidine on the periphery of the CoPc.
- Full Text:
- Date Issued: 2007
- Authors: Obirai, Joseph C , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281403 , vital:55722 , xlink:href="https://doi.org/10.1016/j.jelechem.2006.10.033"
- Description: The electrocatalytic activity of cobalt tetra-2-mercaptopyrimidylphthalocyanine-modified glassy carbon electrode (CoTMPyrPc-GCE) toward gluthathione, L-cysteine and 2-mercaptoethanol has been investigated. CoTMPyrPc-GCE provides a significant improvement on the reported oxidation potential of L-cysteine in pH 4.0 phosphate buffered solution. The oxidation peak potential (Ep), for L-cysteine, was 0.15 V – a relatively lowered oxidation potential compared to reported phthalocyanine complexes. The electrode prepared by drop-dry/thermal annealing method was very stable and sensitive over a long period of time. The stability has been attributed to the thermal annealing and the structure of the mercaptopyrimidine on the periphery of the CoPc.
- Full Text:
- Date Issued: 2007
Tuning the redox properties of metalloporphyrin-and metallophthalocyanine-based molecular electrodes for the highest electrocatalytic activity in the oxidation of thiols
- Bedioui, Fethi, Griveau, Sophie, Nyokong, Tebello, Appleby, A John, Caro, Claudia A, Gulppi, Miguel, Ochoa, Gonzalo, Zagal, José H
- Authors: Bedioui, Fethi , Griveau, Sophie , Nyokong, Tebello , Appleby, A John , Caro, Claudia A , Gulppi, Miguel , Ochoa, Gonzalo , Zagal, José H
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283988 , vital:56009 , xlink:href="https://doi.org/10.1039/B618767F"
- Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
- Full Text:
- Date Issued: 2007
- Authors: Bedioui, Fethi , Griveau, Sophie , Nyokong, Tebello , Appleby, A John , Caro, Claudia A , Gulppi, Miguel , Ochoa, Gonzalo , Zagal, José H
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283988 , vital:56009 , xlink:href="https://doi.org/10.1039/B618767F"
- Description: In this work we discuss different approaches for achieving electrodes modified with N4 macrocyclic complexes for the catalysis of the electrochemical oxidation of thiols. These approaches involve adsorption, electropolymerization and molecular anchoring using self assembled monolayers. We also discuss the parameters that determine the reactivity of these complexes. Catalytic activity is associated with the nature of the central metal, redox potentials and Hammett parameters of substituents on the ligand. Correlations between catalytic activity (log i at constant E) and the redox potential of catalysts for complexes of Cr, Mn, Fe, Co, Ni and Cu are linear with an increase of activity for more positive redox potentials. For a great variety complexes bearing the same metal center (Co) correlations between log i and Eo′ of the Co(II)/Co(I) couple have the shape of an unsymmetric volcano. This indicates that the potential of the Co(II)/Co(I) couple can be tuned using the appropiate ligand to achieve maximum catalytic activity. Maximum activity probably corresponds to a ΔG of adsorption of the thiol on the Co center equal to zero, and to a coverage of active sites by the thiol equal to 0.5.
- Full Text:
- Date Issued: 2007
Voltammetric characterisation of the self-assembled monolayers (SAMs) of benzyl-and dodecyl-mercapto tetra substituted metallophthalocyanines complexes
- Agboola, Bolade, Westbroek, Philippe, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007
- Authors: Agboola, Bolade , Westbroek, Philippe , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281414 , vital:55723 , xlink:href="https://doi.org/10.1016/j.elecom.2006.08.047"
- Description: Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)6 3+ ]/[Fe(H2O)6 2+ ]. The solution chemistry of [Fe(CN)6]−3/[Fe(CN)6]−4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24 h. For SAM formation time at 24 and 48 h, CoTDMPc-SAM showed more inhibition of the [Fe(CN)6]−3/[Fe(CN)6]−4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8 V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.
- Full Text:
- Date Issued: 2007