31P NMR kinetic study of the tandem cleavage of phosphonate esters by bromotrimethylsilane
- Conibear, Anne C, Lobb, Kevin A, Kaye, Perry T
- Authors: Conibear, Anne C , Lobb, Kevin A , Kaye, Perry T
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449304 , vital:74810 , xlink:href="https://doi.org/10.1016/j.tet.2010.08.058"
- Description: 1H and 31P NMR methods have been used to access rate constants and activation parameters for each of the consecutive second-order silylation reactions involved in the overall transformation (1a→3a→4a), while computational optimisation of the rate constants obtained from the initial, linear phase of each reaction has permitted an excellent fit with the experimental data for the entire course of the reaction.
- Full Text:
- Authors: Conibear, Anne C , Lobb, Kevin A , Kaye, Perry T
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/449304 , vital:74810 , xlink:href="https://doi.org/10.1016/j.tet.2010.08.058"
- Description: 1H and 31P NMR methods have been used to access rate constants and activation parameters for each of the consecutive second-order silylation reactions involved in the overall transformation (1a→3a→4a), while computational optimisation of the rate constants obtained from the initial, linear phase of each reaction has permitted an excellent fit with the experimental data for the entire course of the reaction.
- Full Text:
Determining spatial changes in the diet of nearshore suspension-feeders along the South African coastline: stable isotope and fatty acid signatures
- Allan, E Louise, Ambrose, Shan T, Richoux, Nicole B, Froneman, P William
- Authors: Allan, E Louise , Ambrose, Shan T , Richoux, Nicole B , Froneman, P William
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457945 , vital:75697 , xlink:href="https://doi.org/10.1016/j.ecss.2010.02.004"
- Description: Mesoscale oceanographic features, such as upwellings, are known to play an important role in regulating the structure and productivity of nearshore marine communities. Stable isotope (δ13C and δ15N) and fatty acid analyses were employed to assess the influence of an upwelling cell along the south-eastern coastline of southern Africa on the diet of the mussel, Perna perna. Eight sites were sampled: two upstream, three in the vicinity and three downstream of the upwelling cell. Stable isotope and fatty acid signatures indicated that the mussels consumed a diet of detritus derived mainly from macroalgae, diatoms and dinoflagellates. One-way ANOVA on the δ13C and δ15N signatures and the principal component analysis of the fatty acid profiles of the mussels identified distinct groups corresponding to the above mentioned regions. The proportion of diatom biomarkers in the fatty acid profiles decreased downstream of the upwelling region while the proportion of dinoflagellate biomarkers increased. Upwelling regions are typically associated with elevated levels of productivity; however, these systems usually become silicon depleted and result in the replacement of diatoms with dinoflagellates. The highest proportions of the dinoflagellate markers were recorded in the two furthest sites downstream of the upwelling cell. The spatial variation in the diet of the mussels, therefore, appears to reflect the presence of the upwelling cell in the nearshore biology of the region.
- Full Text:
- Authors: Allan, E Louise , Ambrose, Shan T , Richoux, Nicole B , Froneman, P William
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/457945 , vital:75697 , xlink:href="https://doi.org/10.1016/j.ecss.2010.02.004"
- Description: Mesoscale oceanographic features, such as upwellings, are known to play an important role in regulating the structure and productivity of nearshore marine communities. Stable isotope (δ13C and δ15N) and fatty acid analyses were employed to assess the influence of an upwelling cell along the south-eastern coastline of southern Africa on the diet of the mussel, Perna perna. Eight sites were sampled: two upstream, three in the vicinity and three downstream of the upwelling cell. Stable isotope and fatty acid signatures indicated that the mussels consumed a diet of detritus derived mainly from macroalgae, diatoms and dinoflagellates. One-way ANOVA on the δ13C and δ15N signatures and the principal component analysis of the fatty acid profiles of the mussels identified distinct groups corresponding to the above mentioned regions. The proportion of diatom biomarkers in the fatty acid profiles decreased downstream of the upwelling region while the proportion of dinoflagellate biomarkers increased. Upwelling regions are typically associated with elevated levels of productivity; however, these systems usually become silicon depleted and result in the replacement of diatoms with dinoflagellates. The highest proportions of the dinoflagellate markers were recorded in the two furthest sites downstream of the upwelling cell. The spatial variation in the diet of the mussels, therefore, appears to reflect the presence of the upwelling cell in the nearshore biology of the region.
- Full Text:
Electrocatalytic oxidation of amitrole and diuron on iron (II) tetraaminophthalocyanine-single walled carbon nanotube dendrimer
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262611 , vital:53536 , xlink:href="https://doi.org/10.1016/j.electacta.2009.12.051"
- Description: FeTAPc-single walled carbon nanotube (SWCNT) dendrimers are employed as glassy carbon electrode modifiers for the electrocatalytic oxidations of amitrole and diuron. The catalytic rate constants were 4.55 × 103 M−1 s−1 and 1.79 × 104 M−1 s−1 for amitrole and diuron, respectively using chronoamperometric studies. The diffusion constants were found to be 1.52 × 10−4 cm2 s−1 and 1.91 × 10−4 cm2 s−1 for diuron and amitrole, respectively. The linear concentration range for both were from 5.0 × 10−5 to 1.0 × 10−4 M and sensitivities of 0.6603 μA/μM and 0.6641 μA/μM for amitrole and diuron, with corresponding limits of detection of 2.15 × 10−7 and 2.6 × 10−7 M using the 3δ notation, respectively.
- Full Text:
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262611 , vital:53536 , xlink:href="https://doi.org/10.1016/j.electacta.2009.12.051"
- Description: FeTAPc-single walled carbon nanotube (SWCNT) dendrimers are employed as glassy carbon electrode modifiers for the electrocatalytic oxidations of amitrole and diuron. The catalytic rate constants were 4.55 × 103 M−1 s−1 and 1.79 × 104 M−1 s−1 for amitrole and diuron, respectively using chronoamperometric studies. The diffusion constants were found to be 1.52 × 10−4 cm2 s−1 and 1.91 × 10−4 cm2 s−1 for diuron and amitrole, respectively. The linear concentration range for both were from 5.0 × 10−5 to 1.0 × 10−4 M and sensitivities of 0.6603 μA/μM and 0.6641 μA/μM for amitrole and diuron, with corresponding limits of detection of 2.15 × 10−7 and 2.6 × 10−7 M using the 3δ notation, respectively.
- Full Text:
Facile electrocatalytic oxidation of diuron on polymerized nickel hydroxo tetraamino-phthalocyanine modified glassy carbon electrodes
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261269 , vital:53379 , xlink:href="https://doi.org/10.1016/j.talanta.2010.02.037"
- Description: The facile electro-oxidation of diuron occurred at a glassy carbon electrode (GCE) modified with polymerized nickel tetraamino-phthalocyanine (NiTAPc), containing O–Ni–O bridges represented as poly-Ni(OH)TAPc-GCE. The oxidation of diuron occurred at a potential which is 60 mV less than that of poly-NiTAPc (without O–Ni–O bridges) and was accompanied by enhanced catalytic currents. The catalytic rate constant and the diffusion constant were found to be 5.91 × 102 mol−1 L s−1 and 6.43 × 10−6 cm2 s−1, respectively. The linear concentration range of diuron was 3.0 × 10−5 to 3.5 × 10−4 mol L−1 with a limit of detection (LOD) of 3.3 × 10−7 mol L−1 (3δ notation) and a sensitivity of 12.9 A mol−1 L cm−2.
- Full Text:
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261269 , vital:53379 , xlink:href="https://doi.org/10.1016/j.talanta.2010.02.037"
- Description: The facile electro-oxidation of diuron occurred at a glassy carbon electrode (GCE) modified with polymerized nickel tetraamino-phthalocyanine (NiTAPc), containing O–Ni–O bridges represented as poly-Ni(OH)TAPc-GCE. The oxidation of diuron occurred at a potential which is 60 mV less than that of poly-NiTAPc (without O–Ni–O bridges) and was accompanied by enhanced catalytic currents. The catalytic rate constant and the diffusion constant were found to be 5.91 × 102 mol−1 L s−1 and 6.43 × 10−6 cm2 s−1, respectively. The linear concentration range of diuron was 3.0 × 10−5 to 3.5 × 10−4 mol L−1 with a limit of detection (LOD) of 3.3 × 10−7 mol L−1 (3δ notation) and a sensitivity of 12.9 A mol−1 L cm−2.
- Full Text:
Fluorescence quenching and energy transfer in conjugates of quantum dots with zinc and indium tetraamino phthalocyanines
- Britton, Jonathan, Antunes, Edith M, Nyokong, Tebello
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262638 , vital:53539 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.013"
- Description: CdTe QDs capped with mercapto propionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104 M−1. High energy transfer efficiencies were obtained in some cases (as high as 93%), due to the low donor to acceptor distances.
- Full Text:
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262638 , vital:53539 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.013"
- Description: CdTe QDs capped with mercapto propionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104 M−1. High energy transfer efficiencies were obtained in some cases (as high as 93%), due to the low donor to acceptor distances.
- Full Text:
Interaction between nickel hydroxy phthalocyanine derivatives with p-chlorophenol
- Khene, Samson, Lobb, Kevin A, Nyokong, Tebello
- Authors: Khene, Samson , Lobb, Kevin A , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248461 , vital:51688 , xlink:href="https://doi.org/10.1016/j.electacta.2010.10.007"
- Description: In this work the interaction between peripherally (β) substituted nickel tetrahydroxyphthalocyanines (β-NiPc(OH)4 and β-Ni(O)Pc(OH)4) with p-chlorophenol is theoretically rationalised by performing calculations at B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and p-chlorophenol, in order to determine the reactive sites involved when p-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: ads-α-NiPc(OH)8-OPGE (OPGE = ordinary poly graphite electrode), ads-α-NiPc(OH)4-OPGE and ads-β-NiPc(OH)4-OPGE are compared with those of the polymerized counterparts: poly-α-Ni(O)Pc(OH)8-OPGE, poly-α-NiPc(OH)4-OPGE and poly-β-NiPc(OH)4-OPGE, respectively.
- Full Text:
- Authors: Khene, Samson , Lobb, Kevin A , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248461 , vital:51688 , xlink:href="https://doi.org/10.1016/j.electacta.2010.10.007"
- Description: In this work the interaction between peripherally (β) substituted nickel tetrahydroxyphthalocyanines (β-NiPc(OH)4 and β-Ni(O)Pc(OH)4) with p-chlorophenol is theoretically rationalised by performing calculations at B3LYP/6-31G(d) level. Density functional theory (DFT) and molecular orbital theory are used to calculate the condensed Fukui function for phthalocyanine derivatives and p-chlorophenol, in order to determine the reactive sites involved when p-chlorophenol is oxidized, and to compare theoretically predicted reactivity to experimentally determined electrocatalytic activity. Electrocatalytic activities of adsorbed NiPc derivatives: ads-α-NiPc(OH)8-OPGE (OPGE = ordinary poly graphite electrode), ads-α-NiPc(OH)4-OPGE and ads-β-NiPc(OH)4-OPGE are compared with those of the polymerized counterparts: poly-α-Ni(O)Pc(OH)8-OPGE, poly-α-NiPc(OH)4-OPGE and poly-β-NiPc(OH)4-OPGE, respectively.
- Full Text:
Metallophthalocyanine-based molecular materials as catalysts for electrochemical reactions
- Zagal, José H, Griveau, Sophie J, Silva, Francisco, Nyokong, Tebello, Bedioui, Fethi
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
- Authors: Zagal, José H , Griveau, Sophie J , Silva, Francisco , Nyokong, Tebello , Bedioui, Fethi
- Date: 2010
- Language: English
- Type: text , Article
- Identifier: vital:7239 , http://hdl.handle.net/10962/d1019718
- Description: Metallophthalocyanines confined on the surface of electrodes are active catalysts for a large variety of electrochemical reactions and electrode surfaces modified by these complexes can be obtained by simple adsorption on graphite and carbon. However, more stable electrodes can be achieved by coating their surfaces with electropolymerized layers of the complexes, that show similar activity than their monomer counterparts. In all cases, fundamental studies carried out with adsorbed layers of these complexes have shown that the redox potential is a very good reactivity index for predicting the catalytic activity of the complexes. Volcano-shaped correlations have been found between the electrocatalytic activity (as log I at constant E) versus the Co(II)/(I) formal potential (E°′) of Co-macrocyclics for the oxidation of several thiols, hydrazine and glucose. For the electroreduction of O2 only linear correlations between the electrocatalytic activity versus the M(III)/M(II) formal potential have been found using Cr, Mn, Fe and Co phthalocyanines but it is likely that these correlations are “incomplete volcano” correlations. The volcano correlations strongly suggest that E°′, the formal potential of the complex needs to be in a rather narrow potential window for achieving maximum activity, probably corresponding to surface coverages of an M-molecule adduct equal to 0.5 and to standard free energies of adsorption of the reacting molecule on the complex active site equal to zero. These results indicate that the catalytic activity of metallophthalocyanines for the oxidation of several molecules can be “tuned” by manipulating the E°′ formal potential, using proper groups on the macrocyclic ligand. This review emphasizes once more that metallophthalocyanines are extremely versatile materials with many applications in electrocatalysis, electroanalysis, just to mention a few, and they provide very good models for testing their catalytic activity for several reactions. Even though the earlier applications of these complexes were focused on providing active materials for electroreduction of O2, for making active cathodes for fuel cells, the main trend in the literature nowadays is to use these complexes for making active electrodes for electrochemical sensors. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.001
- Full Text: false
Novel, soluble, FluXoro functional substituted zinc phthalocyanines; synthesis, characterization and photophysicochemical properties
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261258 , vital:53378 , xlink:href="https://doi.org/10.1016/j.dyepig.2010.01.001"
- Description: Three novel phthalonitriles and the respective, peripheral tetrakis zinc phthalocyanines were synthesized and characterized using elemental analysis, IR, 1H NMR, mass spectra and electronic spectroscopy. The phthalocyanines displayed good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene. The presence of a long chain fluorine substitituent was found to result in reduced aggregation. The singlet oxygen, photodegradation, fluorescence quantum yield, triplet quantum yield and triplet life time of the complexes in toluene were determined. The effect of fluoro-functional groups on the photophysical and photochemical parameters of the zinc(II) phthalocyanines are also reported. Fluorescence quantum yields for the complexes ranged from 0.021 to 0.041.
- Full Text:
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261258 , vital:53378 , xlink:href="https://doi.org/10.1016/j.dyepig.2010.01.001"
- Description: Three novel phthalonitriles and the respective, peripheral tetrakis zinc phthalocyanines were synthesized and characterized using elemental analysis, IR, 1H NMR, mass spectra and electronic spectroscopy. The phthalocyanines displayed good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene. The presence of a long chain fluorine substitituent was found to result in reduced aggregation. The singlet oxygen, photodegradation, fluorescence quantum yield, triplet quantum yield and triplet life time of the complexes in toluene were determined. The effect of fluoro-functional groups on the photophysical and photochemical parameters of the zinc(II) phthalocyanines are also reported. Fluorescence quantum yields for the complexes ranged from 0.021 to 0.041.
- Full Text:
Optical limiting properties of zinc phthalocyanines in solution and solid PMMA composite films
- Tekin, Sezen, Kürüm, Ulaş, Durmus, Mahmut, Yaglioglu, H Gul, Nyokong, Tebello, Elmali, Ayhan
- Authors: Tekin, Sezen , Kürüm, Ulaş , Durmus, Mahmut , Yaglioglu, H Gul , Nyokong, Tebello , Elmali, Ayhan
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249071 , vital:51775 , xlink:href="https://doi.org/10.1016/j.optcom.2010.07.003"
- Description: The nonlinear absorption and optical limiting (OL) performance of tetra- and octasubstituted zinc phthalocyanine complexes were described in solution and in the solid state using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The polymeric films exhibit a much larger effective nonlinear absorption coefficient in comparison with solution. However, the parameters of the ratio of the excited to ground state absorption cross section and energy-dependent saturation in solution are much better compared to properties in the polymeric film. In terms of the ratio of the excited to ground state absorption cross section, the peripherally substituted complexes show better OL performance than the non-peripherally substituted derivative.
- Full Text:
- Authors: Tekin, Sezen , Kürüm, Ulaş , Durmus, Mahmut , Yaglioglu, H Gul , Nyokong, Tebello , Elmali, Ayhan
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249071 , vital:51775 , xlink:href="https://doi.org/10.1016/j.optcom.2010.07.003"
- Description: The nonlinear absorption and optical limiting (OL) performance of tetra- and octasubstituted zinc phthalocyanine complexes were described in solution and in the solid state using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The polymeric films exhibit a much larger effective nonlinear absorption coefficient in comparison with solution. However, the parameters of the ratio of the excited to ground state absorption cross section and energy-dependent saturation in solution are much better compared to properties in the polymeric film. In terms of the ratio of the excited to ground state absorption cross section, the peripherally substituted complexes show better OL performance than the non-peripherally substituted derivative.
- Full Text:
Photophysical and photochemical parameters of octakis (benzylthio) phthalocyaninato zinc, aluminium and tin
- Akpe, Victor, Brismar, Hjalmar, Nyokong, Tebello, Osadebe, Patience Ogoamak
- Authors: Akpe, Victor , Brismar, Hjalmar , Nyokong, Tebello , Osadebe, Patience Ogoamak
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248472 , vital:51689 , xlink:href="https://doi.org/10.1016/j.molstruc.2010.08.033"
- Description: This paper addresses the synthesis of octa-substituted benzylthio metallophthalocyanines (OBTMPcs) that contain the central metal ions of Zn2+, Al3+ and Sn4+. The ground state absorption of ZnPc(SR)8 (OBTZnPc) along with the ZnPc derivatives, well documented in literature were used to study a new concept called the red shift index (RsI). The concept is based on the empirical values of RsI of the different complexes in solvent media. Unequivocally, parameters used in this paper show strong correlations that are consistent with the results obtained. For instance, RsI of the complexes tend to increase as the refractive index, nD, and solvent donor, DN, of solvent increases. Photodegradation (photobleaching) quantum yield, ϕd measurements of these compounds show that they are highly photostable, ϕd (0.03–0.33 × 10−5). The triplet quantum yield, ϕT (0.40–0.53) and the triplet lifetime, τT (610–810 μs) are within the typical range for metallophthalocyanines in DMSO. The photosensitisation efficiency, SΔ, is relatively high for all the molecules (0.74–0.90).
- Full Text:
- Authors: Akpe, Victor , Brismar, Hjalmar , Nyokong, Tebello , Osadebe, Patience Ogoamak
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/248472 , vital:51689 , xlink:href="https://doi.org/10.1016/j.molstruc.2010.08.033"
- Description: This paper addresses the synthesis of octa-substituted benzylthio metallophthalocyanines (OBTMPcs) that contain the central metal ions of Zn2+, Al3+ and Sn4+. The ground state absorption of ZnPc(SR)8 (OBTZnPc) along with the ZnPc derivatives, well documented in literature were used to study a new concept called the red shift index (RsI). The concept is based on the empirical values of RsI of the different complexes in solvent media. Unequivocally, parameters used in this paper show strong correlations that are consistent with the results obtained. For instance, RsI of the complexes tend to increase as the refractive index, nD, and solvent donor, DN, of solvent increases. Photodegradation (photobleaching) quantum yield, ϕd measurements of these compounds show that they are highly photostable, ϕd (0.03–0.33 × 10−5). The triplet quantum yield, ϕT (0.40–0.53) and the triplet lifetime, τT (610–810 μs) are within the typical range for metallophthalocyanines in DMSO. The photosensitisation efficiency, SΔ, is relatively high for all the molecules (0.74–0.90).
- Full Text:
Photophysical and photochemical properties of Ni (II), Pd (II) and Pt (II) aryloxo and alkylthio derivatised phthalocyanine
- Ogunbayo, Taofeek B, Nyokong, Tebello
- Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261511 , vital:53416 , xlink:href="https://doi.org/10.1016/j.molstruc.2010.03.047"
- Description: Several aryloxo (3a–6a and 3b–6b) and alkylthio (3d and 3e) derivatised phthalocyanines were synthesized, characterized and the photochemical and photophysical properties investigated along with those of the previously reported (3c–5c, 4d, 5d, 4e and 5e) complexes. The effects of open-shell metals (Ni(II), Pd(II) and Pt(II)) on the photophysical and photochemical properties of the phthalocyanine ligands were investigated. Palladium and platinum improved the triplet quantum yield and singlet oxygen generation capacities of the unmetalated phthalocyanines (3a–3e) making their complexes candidates for further investigation in photocatalysis. Ni(II)Pc analogues gave poor results compared with their Pd(II)Pc and Pt(II)Pc counterparts.
- Full Text:
- Authors: Ogunbayo, Taofeek B , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261511 , vital:53416 , xlink:href="https://doi.org/10.1016/j.molstruc.2010.03.047"
- Description: Several aryloxo (3a–6a and 3b–6b) and alkylthio (3d and 3e) derivatised phthalocyanines were synthesized, characterized and the photochemical and photophysical properties investigated along with those of the previously reported (3c–5c, 4d, 5d, 4e and 5e) complexes. The effects of open-shell metals (Ni(II), Pd(II) and Pt(II)) on the photophysical and photochemical properties of the phthalocyanine ligands were investigated. Palladium and platinum improved the triplet quantum yield and singlet oxygen generation capacities of the unmetalated phthalocyanines (3a–3e) making their complexes candidates for further investigation in photocatalysis. Ni(II)Pc analogues gave poor results compared with their Pd(II)Pc and Pt(II)Pc counterparts.
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Photophysical properties of newly synthesized fluorinated zinc phthalocyanines in the presence of CdTe quantum dots and the accompanying energy transfer processes
- Erdoğmuş, Ali, Moeno, Sharon, Litwinski, Christian, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Moeno, Sharon , Litwinski, Christian , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262671 , vital:53543 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.014"
- Description: The photophysical properties of two newly synthesized phthalocyanines (Pcs) were studied in the presence and the absence of 3-mercaptopropionic acid (MPA) capped quantum dots (QDs). Energy transfer processes resulting from the combination of QDs and the Pcs: 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato)zinc(II) (TtfmMPyZnPc, 3) and 4-(tetrakis-5-(trifluoromethyl)-2-pyridyloxyphthalocyaninato) zinc(II) (TtfmPyZnPc, 4) were also studied. The photophysical properties of the Pcs in the presence of QDs were enhanced and Förster resonance energy transfer (FRET) was observed with the phthalocyanines used. The efficiency of FRET between the QDs and TtfmMPyZnPc and TtfmPyZnPc was found to be 0.31% and 0.45% in DMSO and 0.24% and 0.32% in pyridine, respectively. The triplet state quantum yields for TtfmMPyZnPc and TtfmPyZnPc were found to be 0.86 and 0.74 in DMSO and 0.83 and 0.76 in pyridine.
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- Authors: Erdoğmuş, Ali , Moeno, Sharon , Litwinski, Christian , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262671 , vital:53543 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.014"
- Description: The photophysical properties of two newly synthesized phthalocyanines (Pcs) were studied in the presence and the absence of 3-mercaptopropionic acid (MPA) capped quantum dots (QDs). Energy transfer processes resulting from the combination of QDs and the Pcs: 4-(tetrakis-5-(trifluoromethyl)-2-mercaptopyridinephthalocyaninato)zinc(II) (TtfmMPyZnPc, 3) and 4-(tetrakis-5-(trifluoromethyl)-2-pyridyloxyphthalocyaninato) zinc(II) (TtfmPyZnPc, 4) were also studied. The photophysical properties of the Pcs in the presence of QDs were enhanced and Förster resonance energy transfer (FRET) was observed with the phthalocyanines used. The efficiency of FRET between the QDs and TtfmMPyZnPc and TtfmPyZnPc was found to be 0.31% and 0.45% in DMSO and 0.24% and 0.32% in pyridine, respectively. The triplet state quantum yields for TtfmMPyZnPc and TtfmPyZnPc were found to be 0.86 and 0.74 in DMSO and 0.83 and 0.76 in pyridine.
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Photophysical study of a covalently linked quantum dot–low symmetry phthalocyanine conjugate
- Chidawanyika, Wadzanai J U, Litwinski, Christian, Antunes, Edith M, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
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- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
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Remarkable sensitivity for detection of bisphenol A on a gold electrode modified with nickel tetraamino phthalocyanine containing Ni–O–Ni bridges
- Chauke, Vongani, Matemadombo, Fungisai, Nyokong, Tebello
- Authors: Chauke, Vongani , Matemadombo, Fungisai , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261280 , vital:53380 , xlink:href="https://doi.org/10.1016/j.jhazmat.2010.01.061"
- Description: This work reports the electrocatalysis of bisphenol A on Ni(II) tetraamino metallophthalocyanine (NiTAPc) polymer modified gold electrode containing Ni–O–Ni bridges (represented as Ni(OH)TAPc). The Ni(II)TAPc films were electro-transformed in 0.1 mol L−1 NaOH aqueous solution to form ‘O–Ni–O oxo bridges’, forming poly-n-Ni(OH)TAPc (where n is the number of polymerising scans). poly-30-Ni(OH)TAPc, poly-50-Ni(OH)TAPc, poly-70-Ni(OH)TAPc and poly-90-Ni(OH)TAPc films were investigated. The polymeric films were characterised by electrochemical impedance spectroscopy and the charge transfer resistance (RCT) values increased with film thickness. The best catalytic activity for the detection of bisphenol A was on poly-70-Ni(OH)TAPc. Electrode resistance to passivation improved with polymer thickness. The electrocatalytic behaviour of bisphenol A was compared to that of p-nitrophenol in terms of electrode passivation and regeneration. The latter was found to passivate the electrode less than the former. The poly-70-Ni(OH)TAPc modified electrode could reliably detect bisphenol A in a concentration range of 7 × 10−4 to 3 × 10−2 mol L−1 with a limit of detection of 3.68 × 10−9 mol L−1. The sensitivity was 3.26 × 10−4 A mol−1 L cm−2.
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- Authors: Chauke, Vongani , Matemadombo, Fungisai , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261280 , vital:53380 , xlink:href="https://doi.org/10.1016/j.jhazmat.2010.01.061"
- Description: This work reports the electrocatalysis of bisphenol A on Ni(II) tetraamino metallophthalocyanine (NiTAPc) polymer modified gold electrode containing Ni–O–Ni bridges (represented as Ni(OH)TAPc). The Ni(II)TAPc films were electro-transformed in 0.1 mol L−1 NaOH aqueous solution to form ‘O–Ni–O oxo bridges’, forming poly-n-Ni(OH)TAPc (where n is the number of polymerising scans). poly-30-Ni(OH)TAPc, poly-50-Ni(OH)TAPc, poly-70-Ni(OH)TAPc and poly-90-Ni(OH)TAPc films were investigated. The polymeric films were characterised by electrochemical impedance spectroscopy and the charge transfer resistance (RCT) values increased with film thickness. The best catalytic activity for the detection of bisphenol A was on poly-70-Ni(OH)TAPc. Electrode resistance to passivation improved with polymer thickness. The electrocatalytic behaviour of bisphenol A was compared to that of p-nitrophenol in terms of electrode passivation and regeneration. The latter was found to passivate the electrode less than the former. The poly-70-Ni(OH)TAPc modified electrode could reliably detect bisphenol A in a concentration range of 7 × 10−4 to 3 × 10−2 mol L−1 with a limit of detection of 3.68 × 10−9 mol L−1. The sensitivity was 3.26 × 10−4 A mol−1 L cm−2.
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Spectroscopic behavior of cationic metallophthalocyanines in the presence of anionic quantum dots
- Idowu, Mopelola A I, Nyokong, Tebello
- Authors: Idowu, Mopelola A I , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
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- Authors: Idowu, Mopelola A I , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262699 , vital:53545 , xlink:href="https://doi.org/10.1016/j.saa.2009.10.050"
- Description: The interactions and spectroscopic properties between cationic zinc phthalocyanine derivatives (peripherally and non-peripherally tetrasubstituted and peripherally octa substituted with 2-diethylmethylaminoethylsulfanyl (βTZnPc, αTZnPc and βOZnPc)) and CdTe core quantum dots (QDs) capped with mercaptopropionic acid or thioglycolic acid (represented as CdTe@MPA and CdTe@TGA, respectively) have been studied in methanol:water mixture. Strong coupling of MPcs was deduced from the interaction since the UV–vis spectroscopic studies of the ground state complex formed on mixing both components showed loss of the phthalocyanine monomeric band with the formation of a dimeric band (spectrum of aggregated species). The dimerization constants were of the order of 104 M−1.
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Spectroscopic studies of nanostructures of negatively charged free base porphyrin and positively charged tin porphyrins
- George, Reama C, Egharevba, Gabriel O, Nyokong, Tebello
- Authors: George, Reama C , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261661 , vital:53432 , xlink:href="https://doi.org/10.1016/j.poly.2010.01.028"
- Description: Spectroscopic studies were carried out on the homoaggregates of negatively charged free base meso-tetraphenylsulfonated porphyrin ([H2TPPS4]4−) and heteroaggregates of a mixture of protonated ([H4TPPS4]2−) and tin meso-tetra (N-methyl-4-pyridyl) porphyrin ([SnTMPyP]4+). The spectroscopic studies were done to determine the optimal conditions required for the fabrication of porphyrin nanorods by ionic self assembly of two oppositely charged porphyrins. In addition, the various spectral changes of [H4TPPS4]2− with concurrent change in pH and concentration are also investigated. In acid media at pH more than 3, and at concentrations less than 1 × 10−5 M, [H4TPPS4]2− molecules form J aggregates. A mixture of [H4TPPS4]2− and [SnTMPyP]4+ forms heteroaggregates of the J type in acid media. At pH’s 2 to 3, the optimum ratio for the formation of J aggregates is 3:1 and for pH 1, the optimum ratio is 2:1. Transmission electron microscope images of the nanostructures formed show that they are of cylindrical shape.
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- Authors: George, Reama C , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261661 , vital:53432 , xlink:href="https://doi.org/10.1016/j.poly.2010.01.028"
- Description: Spectroscopic studies were carried out on the homoaggregates of negatively charged free base meso-tetraphenylsulfonated porphyrin ([H2TPPS4]4−) and heteroaggregates of a mixture of protonated ([H4TPPS4]2−) and tin meso-tetra (N-methyl-4-pyridyl) porphyrin ([SnTMPyP]4+). The spectroscopic studies were done to determine the optimal conditions required for the fabrication of porphyrin nanorods by ionic self assembly of two oppositely charged porphyrins. In addition, the various spectral changes of [H4TPPS4]2− with concurrent change in pH and concentration are also investigated. In acid media at pH more than 3, and at concentrations less than 1 × 10−5 M, [H4TPPS4]2− molecules form J aggregates. A mixture of [H4TPPS4]2− and [SnTMPyP]4+ forms heteroaggregates of the J type in acid media. At pH’s 2 to 3, the optimum ratio for the formation of J aggregates is 3:1 and for pH 1, the optimum ratio is 2:1. Transmission electron microscope images of the nanostructures formed show that they are of cylindrical shape.
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Syntheses and investigation of the effects of position and nature of substituent on the spectral, electrochemical and spectroelectrochemical properties of new cobalt phthalocyanine complexes
- Akinbulu, Isaac A, Nyokong, Tebello
- Authors: Akinbulu, Isaac A , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261677 , vital:53434 , xlink:href="https://doi.org/10.1016/j.poly.2010.01.004"
- Description: The syntheses of new cobalt phthalocyanine (CoPc) complexes, tetra-substituted with diethylaminoethanethio at the peripheral (complex 3a) and non-peripheral (complex 3b) positions, and with benzylmercapto at the non-peripheral position (complex 5), are reported. The effects of the nature and position of substituent on the spectral, electrochemical and spectroelectrochemical properties of these complexes are investigated. Solution electrochemistry of complex 3a showed three distinctly resolved redox processes attributed to CoIIIPc−2/CoIIPc−2 (E½ = +0.64 V versus Ag|AgCl), CoIIPc−2/CoIPc−2 (E½ = −0.24 V versus Ag|AgCl) and CoIPc−2/CoIPc−3 (E½ = −1.26 V versus Ag|AgCl) species. No ring oxidation was observed in complex 3a. Complex 3b showed both ring-based oxidation, attributed to CoIIIPc−1/CoIIIPc−2 species (Ep = +0.86 V versus Ag|AgCl), and ring-based reduction associated with CoIPc−2/CoIPc−3 species (E½ = −1.46 V versus Ag|AgCl), with the normal metal-based redox processes in CoPc complexes: CoIIIPc−2/CoIIPc−2 (Ep = +0.41 V versus Ag|AgCl) and CoIIPc−2/CoIPc−2 (E½ = −0.38 V versus Ag|AgCl). Solution electrochemistry of complex 5 showed the same type and number of species observed in complex 3a: CoIIIPc−2/CoIIPc−2 (Ep = +0.59 V versus Ag|AgCl), CoIIPc−2/CoIPc−2 (E½ = −0.26 V versus Ag|AgCl) and CoIPc−2/CoIPc−3 (E½ = −1.39 V versus Ag|AgCl) species. These processes were confirmed using spectroelectrochemistry.
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- Authors: Akinbulu, Isaac A , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261677 , vital:53434 , xlink:href="https://doi.org/10.1016/j.poly.2010.01.004"
- Description: The syntheses of new cobalt phthalocyanine (CoPc) complexes, tetra-substituted with diethylaminoethanethio at the peripheral (complex 3a) and non-peripheral (complex 3b) positions, and with benzylmercapto at the non-peripheral position (complex 5), are reported. The effects of the nature and position of substituent on the spectral, electrochemical and spectroelectrochemical properties of these complexes are investigated. Solution electrochemistry of complex 3a showed three distinctly resolved redox processes attributed to CoIIIPc−2/CoIIPc−2 (E½ = +0.64 V versus Ag|AgCl), CoIIPc−2/CoIPc−2 (E½ = −0.24 V versus Ag|AgCl) and CoIPc−2/CoIPc−3 (E½ = −1.26 V versus Ag|AgCl) species. No ring oxidation was observed in complex 3a. Complex 3b showed both ring-based oxidation, attributed to CoIIIPc−1/CoIIIPc−2 species (Ep = +0.86 V versus Ag|AgCl), and ring-based reduction associated with CoIPc−2/CoIPc−3 species (E½ = −1.46 V versus Ag|AgCl), with the normal metal-based redox processes in CoPc complexes: CoIIIPc−2/CoIIPc−2 (Ep = +0.41 V versus Ag|AgCl) and CoIIPc−2/CoIPc−2 (E½ = −0.38 V versus Ag|AgCl). Solution electrochemistry of complex 5 showed the same type and number of species observed in complex 3a: CoIIIPc−2/CoIIPc−2 (Ep = +0.59 V versus Ag|AgCl), CoIIPc−2/CoIPc−2 (E½ = −0.26 V versus Ag|AgCl) and CoIPc−2/CoIPc−3 (E½ = −1.39 V versus Ag|AgCl) species. These processes were confirmed using spectroelectrochemistry.
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Synthesis and electrochemical characterisation of new tantalum (V) alkythio phthalocyanines
- Chauke, Vongani, Nyokong, Tebello
- Authors: Chauke, Vongani , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249093 , vital:51777 , xlink:href="https://doi.org/10.1016/j.ica.2010.05.003"
- Description: The synthesis and electrochemical characterisation of octa-pentylthio (4a) and octa-octylthio (4b) – phthalocyaninato tantalum (III) hydroxide are hereby reported. These TaPc complexes absorb in the near infrared region (∼800 nm in dichloromethane). They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. NMR, mass and infrared spectroscopy and elemental analysis confirmed the structures and purity of the synthesised complexes. The cyclic voltammograms (CVs) showed reversible reduction couples and irreversible oxidation peaks. The latter exhibited adsorption behavior. The reduction processes were observed at −0.74 and −1.13 V (versus Ag|AgCl) for 4a, and −0.67, −1.02 and −1.48 V (versus Ag|AgCl) for 4b. Spectroelectrochemistry confirmed one metal reduction, with the rest of the redox processes being centered on the phthalocyanine ring.
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- Authors: Chauke, Vongani , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249093 , vital:51777 , xlink:href="https://doi.org/10.1016/j.ica.2010.05.003"
- Description: The synthesis and electrochemical characterisation of octa-pentylthio (4a) and octa-octylthio (4b) – phthalocyaninato tantalum (III) hydroxide are hereby reported. These TaPc complexes absorb in the near infrared region (∼800 nm in dichloromethane). They show good solubility in most common solvents especially non-viscous solvents such as dichloromethane and chloroform. NMR, mass and infrared spectroscopy and elemental analysis confirmed the structures and purity of the synthesised complexes. The cyclic voltammograms (CVs) showed reversible reduction couples and irreversible oxidation peaks. The latter exhibited adsorption behavior. The reduction processes were observed at −0.74 and −1.13 V (versus Ag|AgCl) for 4a, and −0.67, −1.02 and −1.48 V (versus Ag|AgCl) for 4b. Spectroelectrochemistry confirmed one metal reduction, with the rest of the redox processes being centered on the phthalocyanine ring.
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Synthesis and photophysical properties of 1, 1′-binaphthol substituted phthalocyanines
- Canlica, Meylude, Nyokong, Tebello
- Authors: Canlica, Meylude , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249148 , vital:51782 , xlink:href="https://doi.org/10.1016/j.ica.2010.06.034"
- Description: We report on the synthesis, characterization and photophysical properties of a new symmetrically tetra substituted {at non-peripheral positions with tetra(1,1′-bi-binaphtoxy)} phthalocyanines containing H2, Mg(II), Al(III)Cl, Si(IV)Cl2 in the central cavity. The synthesized compounds were characterized by the elemental analyses, UV–Vis, FT-IR and 1H NMR spectroscopies. The fluorescence quantum yields, triplet quantum yields and lifetimes of the newly synthesized H2, Mg, Al, and Si phthalocyanines were explored. Triplet quantum yields ranged from 0.24 to 0.54. The triplet lifetime for the silicon phthalocyanine derivative was the highest ever reported for a phthalocyanine (∼3.5 ms).
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- Authors: Canlica, Meylude , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249148 , vital:51782 , xlink:href="https://doi.org/10.1016/j.ica.2010.06.034"
- Description: We report on the synthesis, characterization and photophysical properties of a new symmetrically tetra substituted {at non-peripheral positions with tetra(1,1′-bi-binaphtoxy)} phthalocyanines containing H2, Mg(II), Al(III)Cl, Si(IV)Cl2 in the central cavity. The synthesized compounds were characterized by the elemental analyses, UV–Vis, FT-IR and 1H NMR spectroscopies. The fluorescence quantum yields, triplet quantum yields and lifetimes of the newly synthesized H2, Mg, Al, and Si phthalocyanines were explored. Triplet quantum yields ranged from 0.24 to 0.54. The triplet lifetime for the silicon phthalocyanine derivative was the highest ever reported for a phthalocyanine (∼3.5 ms).
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Synthetic pathways to water-soluble phthalocyanines and close analogs
- Dumoulin, Fabienne, Durmus, Mahmut, Ahsen, Vefa, Nyokong, Tebello
- Authors: Dumoulin, Fabienne , Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249082 , vital:51776 , xlink:href="https://doi.org/10.1016/j.ccr.2010.05.002"
- Description: The different types of water-soluble phthalocyanines are presented and their synthesis is reviewed.
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- Authors: Dumoulin, Fabienne , Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249082 , vital:51776 , xlink:href="https://doi.org/10.1016/j.ccr.2010.05.002"
- Description: The different types of water-soluble phthalocyanines are presented and their synthesis is reviewed.
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