Synthesis, photophysical and nonlinear optical properties of microwave synthesized 4-tetra and octa-substituted lead phthalocyanines
- Modibane, Desmond K, Nyokong, Tebello
- Authors: Modibane, Desmond K , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263452 , vital:53629 , xlink:href="https://doi.org/10.1016/j.poly.2009.03.013"
- Description: This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.80 to 0.86 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and more than 10 μs in the rest of the solvents) were observed due to the presence of heavy atom. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2.
- Full Text:
- Date Issued: 2009
- Authors: Modibane, Desmond K , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263452 , vital:53629 , xlink:href="https://doi.org/10.1016/j.poly.2009.03.013"
- Description: This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.80 to 0.86 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and more than 10 μs in the rest of the solvents) were observed due to the presence of heavy atom. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2.
- Full Text:
- Date Issued: 2009
Characterization of polymeric film of a new manganese phthalocyanine complex octa-substituted with 2-diethylaminoethanethiol, and its use for the electrochemical detection of bentazon
- Akinbulu, Isaac A, Nyokong, Tebello
- Authors: Akinbulu, Isaac A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262568 , vital:53534 , xlink:href="https://doi.org/10.1016/j.electacta.2009.07.074"
- Description: Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to MnIIIPc−1/MnIIIPc−2, MnIIIPc−2/MnIIPc−2 and MnIIPc−2/MnIIPc−3 species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, Rct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10−7 M.
- Full Text:
- Date Issued: 2009
- Authors: Akinbulu, Isaac A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262568 , vital:53534 , xlink:href="https://doi.org/10.1016/j.electacta.2009.07.074"
- Description: Manganese acetate octakis-(2-diethyaminoethanethiol) phthalocyanine (AcMnODEAETPc) was newly synthesized and characterized by spectroscopic and electrochemical methods. Solution electrochemistry of the complex showed three redox processes assigned to MnIIIPc−1/MnIIIPc−2, MnIIIPc−2/MnIIPc−2 and MnIIPc−2/MnIIPc−3 species. The new molecule was polymerized onto a glassy carbon electrode (GCE) to form thin films of different thickness, giving poly-10-AcMnODEAETPc-GCE, poly-20-AcMnODEAETPc-GCE and poly-30-AcMnODEAETPc-GCE, where 10, 20 and 30 represent the number of voltammetry scans during polymerization. Three distinct redox processes were observed on the modified electrode in 0.1 M phosphate buffer solution, pH 5, which confirmed the formation of the polymer. The current signal due to the herbicide, bentazon, was dependent on film thickness; the best signal was obtained on poly-20-AcMnODEAETPc-GCE while poly-10-AcMnODEAETPc-GCE gave the least signal. However, the signals due to the herbicide were better on the different films compared to the bare electrode. Electrochemical impedance spectroscopy (EIS) technique revealed that differences in film thickness offered different charge transfer resistances, Rct, hence difference in current signals for bentazon oxidation were observed on these films. A Tafel slope of 77 mV/decade, obtained for the herbicide on poly-20-AcMnODEAETPc-GCE, denotes a fast one electron transfer followed by a slow chemical step in the electro-oxidation of bentazon. The voltammetry signals of the herbicide on the films indicated the likely involvement of ring-based redox processes in the detection of the herbicide. A plot of background corrected current response, on this film, versus the concentration of bentazon was linear within the range 50–750 μM with a detection limit of 2.48 × 10−7 M.
- Full Text:
- Date Issued: 2009
Synthesis, photophysics and photochemistry of novel tetra (quinoxalinyl) phthalocyaninato zinc (II) complexes
- Erdoğmuş, Ali, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263441 , vital:53628 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.04.007"
- Description: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former's higher fluorescence quantum yield (ΦF) and lower triplet quantum yield (ΦT) than the latter's in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (ΦΔ) values show the same trends as ΦT values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene.
- Full Text:
- Date Issued: 2009
- Authors: Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263441 , vital:53628 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.04.007"
- Description: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former's higher fluorescence quantum yield (ΦF) and lower triplet quantum yield (ΦT) than the latter's in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (ΦΔ) values show the same trends as ΦT values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene.
- Full Text:
- Date Issued: 2009
Opposing responses elicited by positively charged phthalocyanines in the presence of CdTe quantum dots
- Moeno, Sharon, Nyokong, Tebello
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264506 , vital:53740 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.10.027"
- Description: Tetrapositively charged phthalocyanines and CdTe quantum dots (QDs) capped with thioglycolic acid (TGA) and mercaptopropionic acid (MPA) were synthesized. The response of the tetrapositively charged zinc phthalocyanines in the presence of quantum dots was studied. Aggregation and charge transfer were observed for [tetramethyl-2,(3)-[tetra-(2-mercaptopyridinephthalocyaninato)]zinc(II)]4+ (TmTMPyZnPc), however aggregation proved to be the more prominent process of the two. Fluorescence resonance energy transfer (FRET) was observed with [tetramethyl-2,(3)-[tetra-(2- pyridyloxyphthalocyaninato)]zinc(II)]4+ (TmTPyZnPc). In the FRET study the efficiency of FRET with TmTPyZnPc was determined to be 21% for both MPA and TGA capped CdTe QDs. For the charge transfer study the fluorescence of the quantum dots was quenched by the TmTMPyZnPc used, and from these quenching studies the quenching constants, binding constants and number of binding sites on the quantum dots were determined.
- Full Text:
- Date Issued: 2009
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264506 , vital:53740 , xlink:href="https://doi.org/10.1016/j.jphotochem.2008.10.027"
- Description: Tetrapositively charged phthalocyanines and CdTe quantum dots (QDs) capped with thioglycolic acid (TGA) and mercaptopropionic acid (MPA) were synthesized. The response of the tetrapositively charged zinc phthalocyanines in the presence of quantum dots was studied. Aggregation and charge transfer were observed for [tetramethyl-2,(3)-[tetra-(2-mercaptopyridinephthalocyaninato)]zinc(II)]4+ (TmTMPyZnPc), however aggregation proved to be the more prominent process of the two. Fluorescence resonance energy transfer (FRET) was observed with [tetramethyl-2,(3)-[tetra-(2- pyridyloxyphthalocyaninato)]zinc(II)]4+ (TmTPyZnPc). In the FRET study the efficiency of FRET with TmTPyZnPc was determined to be 21% for both MPA and TGA capped CdTe QDs. For the charge transfer study the fluorescence of the quantum dots was quenched by the TmTMPyZnPc used, and from these quenching studies the quenching constants, binding constants and number of binding sites on the quantum dots were determined.
- Full Text:
- Date Issued: 2009
The synthesis, cyclic voltammetry and spectroelectrochemical studies of Co (II) phthalocyanines tetra-substituted at the α and β positions with phenylthio groups
- Nombona, Nolwazi, Nyokong, Tebello
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264529 , vital:53742 , xlink:href="https://doi.org/10.1016/j.dyepig.2008.06.002"
- Description: Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E1/2 = −1.44 V (I), −0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E1/2 = −1.42 V (I), −0.57, −0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to CoIPc−2/CoIPc−3 (I), CoIIPc−2/CoIPc−2 (II), CoIIIPc−2/CoIIPc−2 (III), and CoIIIPc−1/CoIIIPc−2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.
- Full Text:
- Date Issued: 2009
- Authors: Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264529 , vital:53742 , xlink:href="https://doi.org/10.1016/j.dyepig.2008.06.002"
- Description: Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E1/2 = −1.44 V (I), −0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E1/2 = −1.42 V (I), −0.57, −0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to CoIPc−2/CoIPc−3 (I), CoIIPc−2/CoIPc−2 (II), CoIIIPc−2/CoIIPc−2 (III), and CoIIIPc−1/CoIIIPc−2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.
- Full Text:
- Date Issued: 2009
The synthesis and photophysicochemical behaviour of novel water-soluble cationic indium (III) phthalocyanine
- Durmus, Mahmut, Erdoğmuş, Ali, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Durmus, Mahmut , Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263419 , vital:53626 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.01.008"
- Description: The syntheses and characterization of 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) and quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) are described. The ground state electronic absorption spectra, photophysics and photochemistry of both dyes in DMSO as well as that of the quaternized compound in aqueous solution are also presented. A comparison of the photophysical and photochemical parameters of the two dyes revealed that quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) was a better photosensitizer than its unquaternized counterpart. The quantum yield values of fluorescence (ΦF), triplet state formation (ΦT) and singlet oxygen formation (ΦΔ) for the cationic dye were found to be 0.03, 0.68 and 0.66 respectively in DMSO; these values were higher than those for 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III), which exhibited values of 0.02, 0.66 and 0.63, respectively in DMSO. The values for the cationic dye in aq. solution were 0.02, 0.59 and 0.56 respectively, suggesting that the water-soluble quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) offers potential as a photosensitizer in photodynamic therapy treatment.
- Full Text:
- Date Issued: 2009
- Authors: Durmus, Mahmut , Erdoğmuş, Ali , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263419 , vital:53626 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.01.008"
- Description: The syntheses and characterization of 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) and quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) are described. The ground state electronic absorption spectra, photophysics and photochemistry of both dyes in DMSO as well as that of the quaternized compound in aqueous solution are also presented. A comparison of the photophysical and photochemical parameters of the two dyes revealed that quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) was a better photosensitizer than its unquaternized counterpart. The quantum yield values of fluorescence (ΦF), triplet state formation (ΦT) and singlet oxygen formation (ΦΔ) for the cationic dye were found to be 0.03, 0.68 and 0.66 respectively in DMSO; these values were higher than those for 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III), which exhibited values of 0.02, 0.66 and 0.63, respectively in DMSO. The values for the cationic dye in aq. solution were 0.02, 0.59 and 0.56 respectively, suggesting that the water-soluble quaternized 2,3-octakis-(3-pyridyloxyphthalocyaninato) indium(III) offers potential as a photosensitizer in photodynamic therapy treatment.
- Full Text:
- Date Issued: 2009
The syntheses, characterization and fluorescence spectra of novel, octakis (alkylthiophthalocyanato) nickel (II) and palladium (II) complexes
- Ogunbayo, Taofeek Babatunde, Ogunsipe, Abimbola, Nyokong, Tebello
- Authors: Ogunbayo, Taofeek Babatunde , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263386 , vital:53623 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.03.009"
- Description: The syntheses, characterization and fluorescence studies of several {octakis(alkylthio)phthalocyanato} palladium(II) and nickel(II) complexes are presented. The absorption spectra of some of the complexes showed extra peaks which are attributable to non-planar distortion, the extent of which, was found to dependent on alkyl chain length. The fluorescence excitation spectra of the nickel(II) derivatives were not in agreement with their absorption spectra, owing to structural changes upon excitation. Fluorescence quantum yields were very low (more than 1%) for all complexes as a consequence of the open-shell electronic structures of nickel(II) and palladium(II).
- Full Text:
- Date Issued: 2009
- Authors: Ogunbayo, Taofeek Babatunde , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263386 , vital:53623 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.03.009"
- Description: The syntheses, characterization and fluorescence studies of several {octakis(alkylthio)phthalocyanato} palladium(II) and nickel(II) complexes are presented. The absorption spectra of some of the complexes showed extra peaks which are attributable to non-planar distortion, the extent of which, was found to dependent on alkyl chain length. The fluorescence excitation spectra of the nickel(II) derivatives were not in agreement with their absorption spectra, owing to structural changes upon excitation. Fluorescence quantum yields were very low (more than 1%) for all complexes as a consequence of the open-shell electronic structures of nickel(II) and palladium(II).
- Full Text:
- Date Issued: 2009
Synthesis, photophysical and photochemical properties of octa-substituted antimony phthalocyanines
- Modibane, Desmond Kwena, Nyokong, Tebello
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
- Full Text:
- Date Issued: 2009
- Authors: Modibane, Desmond Kwena , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264226 , vital:53711 , xlink:href="https://doi.org/10.1016/j.poly.2008.11.052"
- Description: This work reports on the synthesis and photophysicochemical parameters of unsubstituted [SbIIIPc]+I3- and octa-phenoxy ([SbIIIOPPc]+I3-) and -4-t-butylphenoxy ([SbIIIOTBPPc]+I3-) substituted antimony phthalocyanines. Photophysical and photochemical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide and toluene. The excitation spectra of oxidized antimony (Sb(V)Pc) derivates were similar to absorption spectra. Low fluorescence quantum yields, high triplet quantum yields and low triplet lifetimes were observed as the result of heavy atom (antimony ion).
- Full Text:
- Date Issued: 2009
Solvent and central metal effects on the photophysical and photochemical properties of peripherally tetra mercaptopyridine substituted metallophthalocyanines
- Moeno, Sharon, Nyokong, Tebello
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263522 , vital:53635 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.01.021"
- Description: The synthesis of peripherally tetra 2-mercaptopyridine substituted phthalocyanines containing Si, Ga, Sn and In as central metal ions is reported for the first time in this study. Photophysical and photochemical studies were carried out on these compounds in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Fluorescence quantum yields (ΦF) ranged from 0.012 to 0.2 and triplet quantum yields (ΦT) from 0.54 to 0.89 in dimethylformamide (DMF) and from 0.65 to 0.93 in dimethylsulfoxide (DMSO). The triplet lifetimes ranged from 20 to 130 μs, the low values are due to the heavy atom effects of the central metal. The triplet lifetimes were larger in DMSO when compared with DMF.
- Full Text:
- Date Issued: 2009
- Authors: Moeno, Sharon , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263522 , vital:53635 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.01.021"
- Description: The synthesis of peripherally tetra 2-mercaptopyridine substituted phthalocyanines containing Si, Ga, Sn and In as central metal ions is reported for the first time in this study. Photophysical and photochemical studies were carried out on these compounds in order to determine the potential of the complexes as photosensitizers for use in photodynamic therapy. Fluorescence quantum yields (ΦF) ranged from 0.012 to 0.2 and triplet quantum yields (ΦT) from 0.54 to 0.89 in dimethylformamide (DMF) and from 0.65 to 0.93 in dimethylsulfoxide (DMSO). The triplet lifetimes ranged from 20 to 130 μs, the low values are due to the heavy atom effects of the central metal. The triplet lifetimes were larger in DMSO when compared with DMF.
- Full Text:
- Date Issued: 2009
Synthesis, photophysical and photochemical properties of novel soluble tetra [4-(thiophen-3yl)-phenoxy] phthalocyaninato zinc (II) and Ti (IV) O complexes
- Erdoğmuş, Ali, Nyokong, Tebello
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
- Date Issued: 2009
- Authors: Erdoğmuş, Ali , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263318 , vital:53617 , xlink:href="https://doi.org/10.1016/j.ica.2009.07.015"
- Description: The synthesis, photophysical and photochemical properties of zinc and oxo-titanium phthalocyanine derivatives 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)zinc(II), (2); and 4-(tetra[4-(thiophen-3yl)-phenoxy]phthalocyaninato)oxo-titanium(IV), (3), are described for the first time. These peripherally substituted complexes (2 and 3) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic spectroscopy. The compounds (2 and 3) have good solubility in organic solvents such as CHCl3, DCM, DMSO, DMF, THF and toluene and are not aggregated within a wide concentration range. General trends are described for singlet oxygen, photodegradation, fluorescence quantum yields, triplet quantum yields and triplet life times of these complexes in DMSO, DMF and THF. Compound 2 has higher fluorescence quantum yields, triplet quantum yields and triplet life times than 3, however, the former has lower singlet oxygen quantum yields and photodegradation quantum yields than the latter.
- Full Text:
- Date Issued: 2009
Metal (Co, Fe) tribenzotetraazachlorin–fullerene conjugates
- Ozoemena, Kenneth I, Mamuru, Solomon A, Fukuda, Takamitsu, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Ozoemena, Kenneth I , Mamuru, Solomon A , Fukuda, Takamitsu , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263464 , vital:53630 , xlink:href="https://doi.org/10.1016/j.elecom.2009.04.011"
- Description: Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ∼1 × 108 cm3 mol−1 s−1 and a Tafel slope of −171 mV dec−1.
- Full Text:
- Date Issued: 2009
- Authors: Ozoemena, Kenneth I , Mamuru, Solomon A , Fukuda, Takamitsu , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263464 , vital:53630 , xlink:href="https://doi.org/10.1016/j.elecom.2009.04.011"
- Description: Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ∼1 × 108 cm3 mol−1 s−1 and a Tafel slope of −171 mV dec−1.
- Full Text:
- Date Issued: 2009
Electrostatic self-assembly of quaternized 2,(3)-tetra (oxo-pyridine) phthalocyaninato chloroindium (III) with a series of tetrasulfonated phthalocyanines
- George, Reama C, Durmus, Mahmut, Egharevba, Gabriel O, Nyokong, Tebello
- Authors: George, Reama C , Durmus, Mahmut , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263330 , vital:53618 , xlink:href="https://doi.org/10.1016/j.poly.2009.07.035"
- Description: The self-assembly of oppositely charged phthalocyanines, fabricated using quaternized 2,(3)-tetra(oxo-pyridine) phthalocyaninato chloroindium (III) (QInPyPc) as the positively charge molecule and a series of tetrasulfonate phthalocyanine (MTSPc), M = 2H, Mn, Fe, Co and Ni as negatively charged molecules are reported. The self-assembly results in the formation of heteroaggregates. The metallated sulfonated phthalocyanines form nanorod and nanoleaf shaped structures as evidenced by transmission electron microscopy (TEM). The UV–Vis spectra showed blue shifted Q bands, suggesting that these structures were in a face-to-face arrangement. The Raman spectra of the heteroaggregates showed shifting compared to the spectra of the precursors.
- Full Text:
- Date Issued: 2009
- Authors: George, Reama C , Durmus, Mahmut , Egharevba, Gabriel O , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263330 , vital:53618 , xlink:href="https://doi.org/10.1016/j.poly.2009.07.035"
- Description: The self-assembly of oppositely charged phthalocyanines, fabricated using quaternized 2,(3)-tetra(oxo-pyridine) phthalocyaninato chloroindium (III) (QInPyPc) as the positively charge molecule and a series of tetrasulfonate phthalocyanine (MTSPc), M = 2H, Mn, Fe, Co and Ni as negatively charged molecules are reported. The self-assembly results in the formation of heteroaggregates. The metallated sulfonated phthalocyanines form nanorod and nanoleaf shaped structures as evidenced by transmission electron microscopy (TEM). The UV–Vis spectra showed blue shifted Q bands, suggesting that these structures were in a face-to-face arrangement. The Raman spectra of the heteroaggregates showed shifting compared to the spectra of the precursors.
- Full Text:
- Date Issued: 2009
The formation of self-assembled monolayers of thiophthalocyanine complexes of titanium, vanadium and manganese and their use in l-cysteine electrocatalysis
- Mbambisa, Gcineka, Nombona, Nolwazi, Nyokong, Tebello
- Authors: Mbambisa, Gcineka , Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263375 , vital:53622 , xlink:href="https://doi.org/10.1016/j.microc.2009.04.009"
- Description: Self-assembled monolayers (SAMs) based on octapentylthiophthalocyanine complexes of oxovanadium (IV) (OVOPThPc), titanium(IV) (OTiOPThPc), and manganese (III) acetate (AcMnOPThPc), and of tetraphenylthiophthalocyanine complexes of hydroxo manganese(III) (OHMnTPPc) and oxotitanium(IV) (OTiTPPc) are described. The oxidation of l-cysteine was observed at potentials which ranged from 0.52 V to 0.67 V. The detection limits for l-cysteine analysis were of the order of 10− 7 to 10− 6 M.
- Full Text:
- Date Issued: 2009
- Authors: Mbambisa, Gcineka , Nombona, Nolwazi , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263375 , vital:53622 , xlink:href="https://doi.org/10.1016/j.microc.2009.04.009"
- Description: Self-assembled monolayers (SAMs) based on octapentylthiophthalocyanine complexes of oxovanadium (IV) (OVOPThPc), titanium(IV) (OTiOPThPc), and manganese (III) acetate (AcMnOPThPc), and of tetraphenylthiophthalocyanine complexes of hydroxo manganese(III) (OHMnTPPc) and oxotitanium(IV) (OTiTPPc) are described. The oxidation of l-cysteine was observed at potentials which ranged from 0.52 V to 0.67 V. The detection limits for l-cysteine analysis were of the order of 10− 7 to 10− 6 M.
- Full Text:
- Date Issued: 2009
Diffraction efficiency and I–V characteristics of metal-free phthalocyanine doped nematic liquid crystals
- Köysal, Oguz, Okutan, Mustafa, San, S Eren, Nyokong, Tebello, Durmus, Mahmut
- Authors: Köysal, Oguz , Okutan, Mustafa , San, S Eren , Nyokong, Tebello , Durmus, Mahmut
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263511 , vital:53634 , xlink:href="https://doi.org/10.1016/j.matchemphys.2008.10.056"
- Description: The synthesis and characterization of the tetra-4-benzyloxyphenoxy substituted metal-free phthalocyanine (H2Pc) is reported for the first time. Formation of the photoinduced gratings has been experienced in a metal-free phthalocyanine doped nematic liquid crystal (LC) system and its I–V properties are characterized by electrical measurements. Four samples are prepared at different doping percentages and in homogenously aligned sandwiched geometry. We report the results of two set of experiments on these samples. One of them is the grating diffraction experiment for the analysis of optically induced reorientation process which is a basis for possible holographic applications. Accessible diffraction efficiency is found to be linearly increasing as the amount of the phthalocyanine doping rises. In the scope of the other set of measurements I–V peculiarity of the system is also found to be enhanced and linearly dependent on doping.
- Full Text:
- Date Issued: 2009
- Authors: Köysal, Oguz , Okutan, Mustafa , San, S Eren , Nyokong, Tebello , Durmus, Mahmut
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263511 , vital:53634 , xlink:href="https://doi.org/10.1016/j.matchemphys.2008.10.056"
- Description: The synthesis and characterization of the tetra-4-benzyloxyphenoxy substituted metal-free phthalocyanine (H2Pc) is reported for the first time. Formation of the photoinduced gratings has been experienced in a metal-free phthalocyanine doped nematic liquid crystal (LC) system and its I–V properties are characterized by electrical measurements. Four samples are prepared at different doping percentages and in homogenously aligned sandwiched geometry. We report the results of two set of experiments on these samples. One of them is the grating diffraction experiment for the analysis of optically induced reorientation process which is a basis for possible holographic applications. Accessible diffraction efficiency is found to be linearly increasing as the amount of the phthalocyanine doping rises. In the scope of the other set of measurements I–V peculiarity of the system is also found to be enhanced and linearly dependent on doping.
- Full Text:
- Date Issued: 2009
Synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single wall carbon nanotubes
- Mugadza, Tawanda, Nyokong, Tebello
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263341 , vital:53619 , xlink:href="https://doi.org/10.1016/j.electacta.2009.05.074"
- Description: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2 μA/μM and a limit of detection (LOD) of 1.2 × 10−7 M for 2-mercaptoethanol (2-ME) at pH 4.
- Full Text:
- Date Issued: 2009
- Authors: Mugadza, Tawanda , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263341 , vital:53619 , xlink:href="https://doi.org/10.1016/j.electacta.2009.05.074"
- Description: In this paper we report on the synthesis and characterization of electrocatalytic conjugates of tetraamino cobalt (II) phthalocyanine and single walled carbon nanotubes (CoTAPc–SWCNT-linked) for use as electrode surface modifiers. FTIR, UV–vis and Raman spectroscopies were used to ascertain the chemical linkage between CoTAPc and SWCNT while cyclic voltammetry and rotating disk electrode voltammetry were used to assess the electrocatalytic efficiency of the linked product towards the oxidation of 2-mercaptoethanol. The CoTAPc–SWCNT-linked-GCE demonstrated very good catalytic efficiency relative to CoTAPc–SWCNT-mixed-GCE, CoTAPc-GCE and f-SWCNTs-GCE (functionalised SWCNT). CoTAPc–SWCNT-linked-GCE gave a sensitivity of 0.2 μA/μM and a limit of detection (LOD) of 1.2 × 10−7 M for 2-mercaptoethanol (2-ME) at pH 4.
- Full Text:
- Date Issued: 2009
The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues
- Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
- Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
- Full Text:
- Date Issued: 2009
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263397 , vital:53624 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.06.005"
- Description: The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (ФT) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest ФT values and triplet lifetimes (τT) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.
- Full Text:
- Date Issued: 2009
Characterization of nickel tetrahydroxy phthalocyanine complexes and the electrocatalytic oxidation of 4-chlorophenol
- Khene, Samson M, Lobb, Kevin A, Nyokong, Tebello
- Authors: Khene, Samson M , Lobb, Kevin A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263308 , vital:53616 , xlink:href="https://doi.org/10.1016/j.ica.2009.08.019"
- Description: This work reports on the use of nickel(II) tetrahydroxy (NiPc(OH)4) and (poly-Ni(OH)Pc(OH)4) phthalocyanine complexes as films on ordinary poly graphite electrode (OPGE) for the electrochemical oxidation of 4-chlorophenol (4-CP). The NiPc(OH)4 film was electrotransformed to Ni(OH)Pc(OH)4 film in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridge form. The result showed that the Ni(OH)Pc(OH)4 film on OPGE was more electroactive in terms of increase in current and less catalytic in terms of potential compared to the adsorbed NiPc(OH)4 on OPGE. The reactivity of the two molecules was explained by theoretical calculations. The energies of the frontier orbitals of NiPc(OH)4, Ni(OH)Pc(OH)4 and 4-chlorophenol were calculated using density functional theory (DFT) method. The inter molecular hardness (η) and donor–acceptor hardness (ηDA) of Ni(OH)Pc(OH)4, NiPc(OH)4, Ni(OH)Pc(OH)4/4-chlorophenol and NiPc(OH)4/4-chlorophenol were estimated. The Ni(OH)Pc(OH)4, showed stronger interaction with 4-chlorophenol than NiPc(OH)4. DFT method was also used to model IR and Raman spectrum of H2Pc(OH)4 and NiPc(OH)4.
- Full Text:
- Date Issued: 2009
- Authors: Khene, Samson M , Lobb, Kevin A , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263308 , vital:53616 , xlink:href="https://doi.org/10.1016/j.ica.2009.08.019"
- Description: This work reports on the use of nickel(II) tetrahydroxy (NiPc(OH)4) and (poly-Ni(OH)Pc(OH)4) phthalocyanine complexes as films on ordinary poly graphite electrode (OPGE) for the electrochemical oxidation of 4-chlorophenol (4-CP). The NiPc(OH)4 film was electrotransformed to Ni(OH)Pc(OH)4 film in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridge form. The result showed that the Ni(OH)Pc(OH)4 film on OPGE was more electroactive in terms of increase in current and less catalytic in terms of potential compared to the adsorbed NiPc(OH)4 on OPGE. The reactivity of the two molecules was explained by theoretical calculations. The energies of the frontier orbitals of NiPc(OH)4, Ni(OH)Pc(OH)4 and 4-chlorophenol were calculated using density functional theory (DFT) method. The inter molecular hardness (η) and donor–acceptor hardness (ηDA) of Ni(OH)Pc(OH)4, NiPc(OH)4, Ni(OH)Pc(OH)4/4-chlorophenol and NiPc(OH)4/4-chlorophenol were estimated. The Ni(OH)Pc(OH)4, showed stronger interaction with 4-chlorophenol than NiPc(OH)4. DFT method was also used to model IR and Raman spectrum of H2Pc(OH)4 and NiPc(OH)4.
- Full Text:
- Date Issued: 2009
Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes
- Chidawanyika, Wadzanai J U, Mack, John, Shimizu, Soji, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
The role of macrophytes as a refuge and food source for the estuarine isopod Exosphaeroma hylocoetes ()
- Henninger, Tony O, Froneman, P William, Richoux, Nicole B, Hodgson, Alan N
- Authors: Henninger, Tony O , Froneman, P William , Richoux, Nicole B , Hodgson, Alan N
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/458360 , vital:75735 , xlink:href="https://doi.org/10.1016/j.ecss.2009.01.01"
- Description: The role of submerged macrophytes as refugia from fish predation and as possible food sources for the estuarine isopod Exosphaeroma hylocoetes (Barnard, K.H., 1940) was investigated. Laboratory experiments tested the effectiveness of artificial vegetation, replicating submerged vegetation, in enabling isopods to elude selected fish predators Rhabdosargus holubi, Glossogobius callidus, Monodactylus falciformis and Clinus cottoides. Isopods preferentially hid in the vegetation (>90%), even in absence of fish. The predatory fish had varying success in finding isopods within the vegetation. Isopod mortality ranged from 2% (R. holubi) to a maximum of 87% (C. cottoides) within vegetation, depending on the fish predator present. Stable isotope and fatty acid analyses ruled out the submerged macrophyte Ruppia maritima and inundated fringing grasses as direct food sources, but highlighted the epiphytic biota (mainly diatoms) found on the submerged vegetation and sediments as more likely food sources. These findings are consistent with gut content analyses. The results suggest that the close association of E. hylocoetes with R. maritima is the result of the vegetation providing the isopod with a refuge against fish predation as well as areas of increased food availability.
- Full Text:
- Date Issued: 2009
- Authors: Henninger, Tony O , Froneman, P William , Richoux, Nicole B , Hodgson, Alan N
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/458360 , vital:75735 , xlink:href="https://doi.org/10.1016/j.ecss.2009.01.01"
- Description: The role of submerged macrophytes as refugia from fish predation and as possible food sources for the estuarine isopod Exosphaeroma hylocoetes (Barnard, K.H., 1940) was investigated. Laboratory experiments tested the effectiveness of artificial vegetation, replicating submerged vegetation, in enabling isopods to elude selected fish predators Rhabdosargus holubi, Glossogobius callidus, Monodactylus falciformis and Clinus cottoides. Isopods preferentially hid in the vegetation (>90%), even in absence of fish. The predatory fish had varying success in finding isopods within the vegetation. Isopod mortality ranged from 2% (R. holubi) to a maximum of 87% (C. cottoides) within vegetation, depending on the fish predator present. Stable isotope and fatty acid analyses ruled out the submerged macrophyte Ruppia maritima and inundated fringing grasses as direct food sources, but highlighted the epiphytic biota (mainly diatoms) found on the submerged vegetation and sediments as more likely food sources. These findings are consistent with gut content analyses. The results suggest that the close association of E. hylocoetes with R. maritima is the result of the vegetation providing the isopod with a refuge against fish predation as well as areas of increased food availability.
- Full Text:
- Date Issued: 2009
Characterization of manganese tetraarylthiosubstituted phthalocyanines self assembled monolayers
- Matemadombo, Fungisai, Durmus, Mahmut, Togo, Chamunorwa, Limson, Janice L, Nyokong, Tebello
- Authors: Matemadombo, Fungisai , Durmus, Mahmut , Togo, Chamunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263364 , vital:53621 , xlink:href="https://doi.org/10.1016/j.electacta.2009.04.059"
- Description: Manganese tetraarylthiosubstituted phthalocyanines (complexes 1–5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303–539 μF cm−2) and surface coverage (1.06 × 10−10–2.80 × 10−10 mol cm−2). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1–5 were employed to detect L-cysteine (with limit of detection ranging from 2.83 × 10−7 to 3.14 × 10−7 M at potentials of 0.68–0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 × 10−7 to 3.02 × 10−7 M at potentials of 0.69–0.76 V vs. Ag|AgCl).
- Full Text:
- Date Issued: 2009
- Authors: Matemadombo, Fungisai , Durmus, Mahmut , Togo, Chamunorwa , Limson, Janice L , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263364 , vital:53621 , xlink:href="https://doi.org/10.1016/j.electacta.2009.04.059"
- Description: Manganese tetraarylthiosubstituted phthalocyanines (complexes 1–5) have been deposited on Au electrode surfaces through the self assembled monolayer (SAM) technique. SAM characteristics reported in this work are: ion barrier factor (∼1); interfacial capacitance (303–539 μF cm−2) and surface coverage (1.06 × 10−10–2.80 × 10−10 mol cm−2). Atomic force microscopy was employed in characterizing a SAM. SAMs of complexes 1–5 were employed to detect L-cysteine (with limit of detection ranging from 2.83 × 10−7 to 3.14 × 10−7 M at potentials of 0.68–0.75 V vs. Ag|AgCl) and nitrite (limit of detection ranging from 1.78 × 10−7 to 3.02 × 10−7 M at potentials of 0.69–0.76 V vs. Ag|AgCl).
- Full Text:
- Date Issued: 2009