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.
- Full Text:
- Date Issued: 2010
- 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.
- Full Text:
- Date Issued: 2010
Probing electrochemical and electrocatalytic properties of cobalt (II) and manganese (III) octakis (hexylthio) phthalocyanine as self-assembled monolayers
- Mashazi, Philani N, Antunes, Edith M, Nyokong, Tebello
- Authors: Mashazi, Philani N , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249115 , vital:51779 , xlink:href="https://doi.org/10.1142/S108842461000277X"
- Description: New peripherally (β) and non-peripherally (α) substituted metal octakis(hexylthio)phthalocyanines (β- and α-MOcHexTPc) containing cobalt and manganese as metal centers were synthesized. Their characterization using electrochemical methods showed that these complexes exhibit several redox processes at E1/2 (mV vs. Ag∣AgCl) = 380 (212) (I), 1140 (864) (II), -450 (-460) (III) and -1170 (-1304) (IV) for β- (α-) CoOcHexTPc. These redox processes were assigned to CoIIIPc-2/CoIIPc-2 (I), CoIIIPc-1/CoIIIPc-2 (II), CoIIPc-2/CoIPc-2 (III) and CoIPc-2/CoIPc-3 (IV) using spectroelectrochemistry. For the β- (α-) MnOcHexTPc complex the redox processes were observed at E1/2 (mV vs. Ag∣AgCl) = -20 (5) (I), -530 (-640) (II) and -1270 (-1380) (III) and were assigned to MnIIIPc-2/MnIIPc-2 (I), MnIIPc-2/MnIIPc-3 (II) and MnIIPc-3/MnIIPc-4 (III). Electrochemical and microscopic characterization using AFM showed that the self-assembled monolayers (SAMs) are formed on the gold surface using these complexes. The electrochemical characterization showed the blocking of the Faradaic processes at SAMs modified electrodes and these reactions are well-known to easily occur at unmodified gold electrodes. The AFM characterization showed an increase in surface roughness upon modifying the gold surface with MOcHexTPc SAMs, further confirming the presence of the monolayers on the gold surface. The MOcHexTPc SAMs were investigated for their electrocatalytic application towards H2O2 detection. The MOcHexTPc SAMs modified gold electrodes gave excellent currents for H2O2 detection. The observed H2O2 electrocatalytic reduction peaks were close to where the metal redox processes from the MOcHexTPc occurred, showing the involvement of the metal redox processes in the electrocatalytic mediation reactions.
- Full Text:
- Date Issued: 2010
- Authors: Mashazi, Philani N , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249115 , vital:51779 , xlink:href="https://doi.org/10.1142/S108842461000277X"
- Description: New peripherally (β) and non-peripherally (α) substituted metal octakis(hexylthio)phthalocyanines (β- and α-MOcHexTPc) containing cobalt and manganese as metal centers were synthesized. Their characterization using electrochemical methods showed that these complexes exhibit several redox processes at E1/2 (mV vs. Ag∣AgCl) = 380 (212) (I), 1140 (864) (II), -450 (-460) (III) and -1170 (-1304) (IV) for β- (α-) CoOcHexTPc. These redox processes were assigned to CoIIIPc-2/CoIIPc-2 (I), CoIIIPc-1/CoIIIPc-2 (II), CoIIPc-2/CoIPc-2 (III) and CoIPc-2/CoIPc-3 (IV) using spectroelectrochemistry. For the β- (α-) MnOcHexTPc complex the redox processes were observed at E1/2 (mV vs. Ag∣AgCl) = -20 (5) (I), -530 (-640) (II) and -1270 (-1380) (III) and were assigned to MnIIIPc-2/MnIIPc-2 (I), MnIIPc-2/MnIIPc-3 (II) and MnIIPc-3/MnIIPc-4 (III). Electrochemical and microscopic characterization using AFM showed that the self-assembled monolayers (SAMs) are formed on the gold surface using these complexes. The electrochemical characterization showed the blocking of the Faradaic processes at SAMs modified electrodes and these reactions are well-known to easily occur at unmodified gold electrodes. The AFM characterization showed an increase in surface roughness upon modifying the gold surface with MOcHexTPc SAMs, further confirming the presence of the monolayers on the gold surface. The MOcHexTPc SAMs were investigated for their electrocatalytic application towards H2O2 detection. The MOcHexTPc SAMs modified gold electrodes gave excellent currents for H2O2 detection. The observed H2O2 electrocatalytic reduction peaks were close to where the metal redox processes from the MOcHexTPc occurred, showing the involvement of the metal redox processes in the electrocatalytic mediation reactions.
- Full Text:
- Date Issued: 2010
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.
- Full Text:
- Date Issued: 2010
- 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.
- Full Text:
- Date Issued: 2010
Spectroscopic behavior of cationic metallophthalocyanines in the presence of anionic quantum dots
- Idowu, Mopelola, Nyokong, Tebello
- Authors: Idowu, Mopelola , 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.
- Full Text:
- Date Issued: 2010
- Authors: Idowu, Mopelola , 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.
- Full Text:
- Date Issued: 2010
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.
- Full Text:
- Date Issued: 2010
- 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.
- Full Text:
- Date Issued: 2010
Symmetrically and unsymmetrically substituted carboxy phthalocyanines as sensitizers for nanoporous ZnO films
- Masilela, Nkosiphile, Nombona, Nolwazi, Loewenstein, Thomas, Nyokong, Tebello, Schlettwein, Derck
- Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
- Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
- Full Text:
- Date Issued: 2010
- Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
- Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
- Full Text:
- Date Issued: 2010
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.
- Full Text:
- Date Issued: 2010
- 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.
- Full Text:
- Date Issued: 2010
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.
- Full Text:
- Date Issued: 2010
- 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.
- Full Text:
- Date Issued: 2010
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).
- Full Text:
- Date Issued: 2010
- 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).
- Full Text:
- Date Issued: 2010
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.
- Full Text:
- Date Issued: 2010
- 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.
- Full Text:
- Date Issued: 2010
The effects of point of substitution on the electrochemical behavior of new manganese phthalocyanines, tetra-substituted with diethylaminoethanethiol
- Akinbulu, Isaac Adebayo, Nyokong, Tebello
- Authors: Akinbulu, Isaac Adebayo , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249137 , vital:51781 , xlink:href="https://doi.org/10.1016/j.ica.2010.06.003"
- Description: The syntheses and comparative studies of the spectral, voltammetry and spectroelectrochemical properties of new manganese phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the peripheral (complex 3a) and non-peripheral positions (complex 3b) are reported. Solution electrochemistry of complex 3a showed quasi-reversible metal-based (MnIIIPc−2/MnIIPc−2, E1/2 = −0.07 V vs. Ag|AgCl) and ring-based (MnIIPc−2/MnIIPc−3, E1/2 = −0.78 V vs. Ag|AgCl) reductions, but no ring-based oxidation. However, complex 3b showed weak irreversible ring-oxidation signal (Ep = +0.86 vs. Ag|AgCl). Reversible metal-based (MnIIIPc−2/MnIIPc−2, E1/2 = −0.04 V vs. Ag|AgCl) and ring-based (MnIIPc−2/MnIIPc−3, E1/2 = −0.68 V vs. Ag|AgCl) reductions were also observed for complex 3b. Spectroelectrochemistry was used to confirm these processes. Reduction process involving the metal (MnIIIPc−2/MnIIPc−2) was associated with the formation of manganese μ-oxo complex in complex 3a.
- Full Text:
- Date Issued: 2010
- Authors: Akinbulu, Isaac Adebayo , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249137 , vital:51781 , xlink:href="https://doi.org/10.1016/j.ica.2010.06.003"
- Description: The syntheses and comparative studies of the spectral, voltammetry and spectroelectrochemical properties of new manganese phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the peripheral (complex 3a) and non-peripheral positions (complex 3b) are reported. Solution electrochemistry of complex 3a showed quasi-reversible metal-based (MnIIIPc−2/MnIIPc−2, E1/2 = −0.07 V vs. Ag|AgCl) and ring-based (MnIIPc−2/MnIIPc−3, E1/2 = −0.78 V vs. Ag|AgCl) reductions, but no ring-based oxidation. However, complex 3b showed weak irreversible ring-oxidation signal (Ep = +0.86 vs. Ag|AgCl). Reversible metal-based (MnIIIPc−2/MnIIPc−2, E1/2 = −0.04 V vs. Ag|AgCl) and ring-based (MnIIPc−2/MnIIPc−3, E1/2 = −0.68 V vs. Ag|AgCl) reductions were also observed for complex 3b. Spectroelectrochemistry was used to confirm these processes. Reduction process involving the metal (MnIIIPc−2/MnIIPc−2) was associated with the formation of manganese μ-oxo complex in complex 3a.
- Full Text:
- Date Issued: 2010
The effects of point of substitution on the formation of manganese phthalocyanine-based molecular materials
- Akinbulu, Isaac Adebayo, Khene, Samson, Nyokong, Tebello
- Authors: Akinbulu, Isaac Adebayo , Khene, Samson , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249103 , vital:51778 , xlink:href="https://doi.org/10.1016/j.tsf.2010.08.145"
- Description: Molecular films of manganese phthalocyanine (MnPc) complexes, tetra-substituted with 2-diethylaminoethanethio at the peripheral (Mn(OAc)-β-TDEAETPc, 1) and non-peripheral (Mn(OAc)-α-TDEAETPc, 2) positions were formed on glassy carbon electrode by electropolymerization and electrodeposition respectively. Atomic force microscopy images confirmed the presence of the films and revealed significant morphological differences. The films exhibited an electrocatalytic activity towards the oxidation of the insecticide, bendiocarb. Hydrodynamic technique, using rotating disc electrode voltammetry, was used to investigate the kinetics of electro-oxidation of the insecticide. Morphological differences of the films significantly influenced kinetic parameters. Values of Tafel slopes, obtained from Tafel plots, suggested that catalysis of bendiocarb occurred via outer sphere mechanism.
- Full Text:
- Date Issued: 2010
- Authors: Akinbulu, Isaac Adebayo , Khene, Samson , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249103 , vital:51778 , xlink:href="https://doi.org/10.1016/j.tsf.2010.08.145"
- Description: Molecular films of manganese phthalocyanine (MnPc) complexes, tetra-substituted with 2-diethylaminoethanethio at the peripheral (Mn(OAc)-β-TDEAETPc, 1) and non-peripheral (Mn(OAc)-α-TDEAETPc, 2) positions were formed on glassy carbon electrode by electropolymerization and electrodeposition respectively. Atomic force microscopy images confirmed the presence of the films and revealed significant morphological differences. The films exhibited an electrocatalytic activity towards the oxidation of the insecticide, bendiocarb. Hydrodynamic technique, using rotating disc electrode voltammetry, was used to investigate the kinetics of electro-oxidation of the insecticide. Morphological differences of the films significantly influenced kinetic parameters. Values of Tafel slopes, obtained from Tafel plots, suggested that catalysis of bendiocarb occurred via outer sphere mechanism.
- Full Text:
- Date Issued: 2010
The synthesis and fluorescence behaviour of phthalocyanines unsymmetrically substituted with naphthol and carboxy groups
- Nombona, Nolwazi, Antunes, Edith M, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261534 , vital:53418 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.11.010"
- Description: Unsymmetrically substituted phthalocyanines 8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanine, [8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanato]zinc(II), 8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyanine and [8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenoxy)phthalocyanato]zinc(II) were prepared using the mixed phthalonitrile cyclotetramerization of 3-(1-naphthoxy) phthalonitrile with a carboxylic acid phthalonitrile. The phthalocyanines were separated using column chromatography employing a mixture of THF, ammonia and water. The novel compounds were characterized using UV–Vis, IR, 1H NMR and mass spectrometry as well as elemental analysis. Fluorescence quantum yields were found to range from 0.05 to 0.16.
- Full Text:
- Date Issued: 2010
- Authors: Nombona, Nolwazi , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261534 , vital:53418 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.11.010"
- Description: Unsymmetrically substituted phthalocyanines 8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanine, [8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanato]zinc(II), 8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyanine and [8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenoxy)phthalocyanato]zinc(II) were prepared using the mixed phthalonitrile cyclotetramerization of 3-(1-naphthoxy) phthalonitrile with a carboxylic acid phthalonitrile. The phthalocyanines were separated using column chromatography employing a mixture of THF, ammonia and water. The novel compounds were characterized using UV–Vis, IR, 1H NMR and mass spectrometry as well as elemental analysis. Fluorescence quantum yields were found to range from 0.05 to 0.16.
- Full Text:
- Date Issued: 2010
The synthesis and photophysical properties of novel cationic tetra pyridiloxy substituted aluminium, silicon and titanium phthalocyanines in water
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249159 , vital:51783 , xlink:href="https://doi.org/10.1016/j.jlumin.2010.04.011"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.
- Full Text:
- Date Issued: 2010
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249159 , vital:51783 , xlink:href="https://doi.org/10.1016/j.jlumin.2010.04.011"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.
- Full Text:
- Date Issued: 2010
The synthesis and photophysical properties of water soluble tetrasulfonated, octacarboxylated and quaternised 2,(3)-tetra-(2 pyridiloxy) Ga phthalocyanines
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Language: English
- Type: Article
- Identifier: vital:6579 , http://hdl.handle.net/10962/d1004142
- Description: The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.
- Full Text:
- Date Issued: 2010
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Language: English
- Type: Article
- Identifier: vital:6579 , http://hdl.handle.net/10962/d1004142
- Description: The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.
- Full Text:
- Date Issued: 2010
Tuning the physico-electrochemical properties of novel cobalt (II) octa [(3, 5-biscarboxylate)-phenoxy] phthalocyanine complex using phenylamine-functionalised SWCNTs
- Agboola, Bolade O, Ozoemena, Kenneth I, Nyokong, Tebello, Fukuda, Takamitsu, Kobayashi, Nagao
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261692 , vital:53435 , xlink:href="https://doi.org/10.1016/j.carbon.2009.10.023"
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode.
- Full Text:
- Date Issued: 2010
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261692 , vital:53435 , xlink:href="https://doi.org/10.1016/j.carbon.2009.10.023"
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode.
- Full Text:
- Date Issued: 2010