Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Nwaji, Njemuwa, Oluwole, David O, Mack, John, Louzada, Marcel, Khene, Samson M, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
Spectroscopic and nonlinear optical properties of alkyl thio substituted binuclear phthalocyanines
- Makinde, Zainab O, Louzada, Marcel S, Britton, Jonathan, Nyokong, Tebello, Khene, Samson M
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
- Full Text:
- Date Issued: 2019
- Authors: Makinde, Zainab O , Louzada, Marcel S , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187485 , vital:44661 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.10.022"
- Description: This work presents the spectroscopic and nonlinear optical properties of metal free binuclear and monomeric 4- (pentylthio)phthalocyanine and cobalt 4,5-(bipentylthio)phthalocyanine. Second order nonlinear absorption coefficient (β) values for the complexes were determined and compared.
- Full Text:
- Date Issued: 2019
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
Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol
- Makinde, Zainab O, Louzada, Marcel, Mashazi, Philani N, Nyokong, Tebello, Khene, Samson M
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
- Full Text:
- Date Issued: 2017
- Authors: Makinde, Zainab O , Louzada, Marcel , Mashazi, Philani N , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188138 , vital:44726 , xlink:href="https://doi.org/10.1016/j.apsusc.2017.06.271"
- Description: Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.
- Full Text:
- Date Issued: 2017
Exploiting Click Chemistry for the Covalent Immobilization of Tetra (4-Propargyloxyphenoxy) Metallophthalocyanines onto Phenylazide-Grafted Gold Surfaces
- Mwanza, Daniel, Mvango, Sindisiwe, Khene, Samson M, Nyokong, Tebello, Mashazi, Philani N
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
- Authors: Mwanza, Daniel , Mvango, Sindisiwe , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189177 , vital:44824 , xlink:href="https://doi.org/10.1016/j.electacta.2017.09.115"
- Description: In this study, tetra-(4-propargyloxy)phenoxy phthalocyanines (MTPrOPhOPc) were covalently immobilized as thin films onto gold surfaces via click reaction. The gold electrode surfaces were pre-functionalized with phenylazide (Au-PAz) thin film using in-situ diazonium generation followed by electrografting. Copper (I) catalyzed alkynyl-azide cycloaddition (CuCAAC) reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. Au-PAz-MTPrOPhOPc exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and spectroscopic surface characterization of the functionalized gold electrode surfaces confirmed the presence of the phenylazide and MTPrOPhOPc thin monolayer films. The excellent electroanalysis of hydrogen peroxide with the limit of detection (LoD) and limit of quantification (LoQ) in the μM range was obtained. The electrocatalytic reduction peaks for H2O2 were observed at −0.37 V for Au-PAz-Mn(OAc)TPrOPhOPc and −0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-Mn(OAc)TPrOPhOPc and Au-PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution.
- Full Text:
- Date Issued: 2017
Fluorescence behavior of glutathione capped CdTe@ ZnS quantum dots chemically coordinated to zinc octacarboxy phthalocyanines
- Sekhosana, Kutloano E, Antunes, Edith M, Khene, Samson M, D'Souza, Sarah, Nyokong, Tebello
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
- Full Text:
- Date Issued: 2013
- Authors: Sekhosana, Kutloano E , Antunes, Edith M , Khene, Samson M , D'Souza, Sarah , Nyokong, Tebello
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242019 , vital:50993 , xlink:href="https://doi.org/10.1016/j.jlumin.2012.11.044"
- Description: Core–shell CdTe@ZnS quantum dots capped with glutathione (CdTe@ZnS–GSH) were covalently linked to zinc octacarboxy phthalocyanine (ZnPc(COOH)8). The conjugate was characterized by UV/Vis, infrared and X-Ray photoelectron spectroscopies as well as transmission electron and atomic force microscopies. The fluorescence quantum yields of the core CdTe capped with thioglycolic acid increased upon formation of the core-shell. Upon conjugation with ZnPc(COOH)8, the fluorescence quantum yield of CdTe@ZnS–GSH decreased due to energy transfer from the latter to the Pc. The average fluorescence lifetime of the CdTe@ZnS–GSH QD also decreased upon conjugation from 26.2 to 13.3 ns.
- Full Text:
- Date Issued: 2013
The development of catalytic oxovanadium (IV)-containing microspheres for the oxidation of various organosulfur compounds
- Ogunlaja, Adeniyi S, Khene, Samson M, Antunes, Edith M, Nyokong, Tebello, Torto, Nelson, Tshentu, Zenixole R
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
- Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
- Date: 2013
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
- Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
- Full Text:
- Date Issued: 2013
Enhanced optical limiting performance in phthalocyanine-quantum dot nanocomposites by free-carrier absorption mechanism
- Sanusi, Kayode, Khene, Samson M, Nyokong, Tebello
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
- Full Text:
- Date Issued: 2014
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
- Full Text:
- Date Issued: 2014
Photophysical and nonlinear optical properties of the positional isomers of 4-(4-tertbutylphenoxy) substituted cobalt, nickel and copper phthalocyanines
- Neduvhuledza, Zelda, Nkaki, Thabo, Louzada, Marcel, Nyokong, Tebello, Khene, Samson M
- Authors: Neduvhuledza, Zelda , Nkaki, Thabo , Louzada, Marcel , Nyokong, Tebello , Khene, Samson M
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186067 , vital:44460 , xlink:href="https://doi.org/10.1016/j.optmat.2020.110195"
- Description: This paper reports on the third order nonlinear optical properties of cobalt, nickel and tetrakis(4- terbutylphenoxy)phthalocyaninatocopper(II) isomers, using the Z-scan technique. Metal-free isomers were found to have high nonlinear absorption coefficient (β) values compared to the metalated isomers. Metal-free C2v isomer was found to have the highest β value of 1.52 × 10− 10 mMW− 1 in THF. All the metal-free and metal phthalocyanine isomers nonlinear properties were found to be dependent on the singlet state absorption. Imaginary second order nonlinear hyperpolarizability (Im[γ]), ground state cross section (σg), excited states cross sections (σs and σt) and two photon absorption (TPA) cross section (σTPA) values are reported in this work. The five-energy level model rate equations were used to model the nonlinear response and absorption cross sections.
- Full Text:
- Date Issued: 2020
- Authors: Neduvhuledza, Zelda , Nkaki, Thabo , Louzada, Marcel , Nyokong, Tebello , Khene, Samson M
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186067 , vital:44460 , xlink:href="https://doi.org/10.1016/j.optmat.2020.110195"
- Description: This paper reports on the third order nonlinear optical properties of cobalt, nickel and tetrakis(4- terbutylphenoxy)phthalocyaninatocopper(II) isomers, using the Z-scan technique. Metal-free isomers were found to have high nonlinear absorption coefficient (β) values compared to the metalated isomers. Metal-free C2v isomer was found to have the highest β value of 1.52 × 10− 10 mMW− 1 in THF. All the metal-free and metal phthalocyanine isomers nonlinear properties were found to be dependent on the singlet state absorption. Imaginary second order nonlinear hyperpolarizability (Im[γ]), ground state cross section (σg), excited states cross sections (σs and σt) and two photon absorption (TPA) cross section (σTPA) values are reported in this work. The five-energy level model rate equations were used to model the nonlinear response and absorption cross sections.
- Full Text:
- Date Issued: 2020
Optical limiting properties of indium 5, 10, 15, 20-tetrakis (4-aminophenyl) porphyrin covalently linked to semiconductor quantum dots
- Managa, Muthumuni, Mgidlana, Sithi, Khene, Samson M, Nyokong, Tebello
- Authors: Managa, Muthumuni , Mgidlana, Sithi , Khene, Samson M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186101 , vital:44463 , xlink:href="https://doi.org/10.1016/j.ica.2020.119838"
- Description: 5,10,15,20-tetrakis(4-aminophenyl) porphyrin and it indium derivative were synthesised and characterized then covalently linked to CdTe/ZnSe/ZnO semiconductor quantum dots. The nonlinear absorption of the complexes was studied using the Z-scan technique at 532 nm and 10 ns pulse in dimethyl sulfoxide. Indium 5,10,15,20- tetrakis(4-aminophenyl) porphyrin (InTAPP) exhibited the strongest nonlinear optical behaviour in comparison with the metal free derivative. DFT calculations were carried out using SDD basis set at B3LYP level of theory. The nonlinear absorption coefficient (βeff) values were determined experimentally using Z-scan whereby the first static hyperpolarizability (βHRS) value were determined using DFT calcutions.
- Full Text:
- Date Issued: 2020
- Authors: Managa, Muthumuni , Mgidlana, Sithi , Khene, Samson M , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186101 , vital:44463 , xlink:href="https://doi.org/10.1016/j.ica.2020.119838"
- Description: 5,10,15,20-tetrakis(4-aminophenyl) porphyrin and it indium derivative were synthesised and characterized then covalently linked to CdTe/ZnSe/ZnO semiconductor quantum dots. The nonlinear absorption of the complexes was studied using the Z-scan technique at 532 nm and 10 ns pulse in dimethyl sulfoxide. Indium 5,10,15,20- tetrakis(4-aminophenyl) porphyrin (InTAPP) exhibited the strongest nonlinear optical behaviour in comparison with the metal free derivative. DFT calculations were carried out using SDD basis set at B3LYP level of theory. The nonlinear absorption coefficient (βeff) values were determined experimentally using Z-scan whereby the first static hyperpolarizability (βHRS) value were determined using DFT calcutions.
- Full Text:
- Date Issued: 2020
Photophysical and nonlinear optical characteristics of pyridyl substituted phthalocyanine-detonation nanodiamond conjugated systems in solution
- Matshitse, Refilwe, Khene, Samson M, Nyokong, Tebello
- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
- Full Text:
- Date Issued: 2019
- Authors: Matshitse, Refilwe , Khene, Samson M , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187079 , vital:44563 , xlink:href="https://doi.org/10.1016/j.diamond.2019.03.013"
- Description: In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.
- Full Text:
- Date Issued: 2019
Electrochemical and photophysical characterization of non-peripherally-octaalkyl substituted dichlorotin (IV) phthalocyanine and tetrabenzotriazaporphyrin compounds
- Khene, Samson M, Cammidge, Andrew N, Cook, Michael J, Nyokong, Tebello
- Authors: Khene, Samson M , Cammidge, Andrew N , Cook, Michael J , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271216 , vital:54522 , xlink:href="https://doi.org/10.1142/S1088424607000886"
- Description: Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (3a), octahexyltetrabenzo-5,10,15- triazaporphyrinato dichlorotin(IV) (3b) and octadecylphthalocyaninato dichlorotin(IV) (3c) were synthesized and their photophysical and electrochemical behavior studied. Complex 3b, containing a CH group in place of one of the aza nitrogen atoms of the phthalocyanine core, shows a split Q-band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (3a and 3c). In contrast, 3b shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in tetrahydrofuran than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring-based redox processes.
- Full Text:
- Date Issued: 2007
- Authors: Khene, Samson M , Cammidge, Andrew N , Cook, Michael J , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271216 , vital:54522 , xlink:href="https://doi.org/10.1142/S1088424607000886"
- Description: Three non-peripherally substituted tin(IV) macrocylic compounds, octahexylphthalocyaninato dichlorotin(IV) (3a), octahexyltetrabenzo-5,10,15- triazaporphyrinato dichlorotin(IV) (3b) and octadecylphthalocyaninato dichlorotin(IV) (3c) were synthesized and their photophysical and electrochemical behavior studied. Complex 3b, containing a CH group in place of one of the aza nitrogen atoms of the phthalocyanine core, shows a split Q-band due to its lower symmetry. The triplet state quantum yields were found to be lower than would be expected on the basis of the heavy atom effect of tin as the central metal for phthalocyanine derivatives (3a and 3c). In contrast, 3b shows a triplet quantum yield ΦT = 0.78. The triplet state lifetimes were solvent dependent, and were higher in tetrahydrofuran than in toluene. Cyclic voltammetry and spectroelectrochemistry of the complexes revealed only ring-based redox processes.
- Full Text:
- Date Issued: 2007
Photooxidation of 4-chlorophenol sensitized by lutetium tetraphenoxy phthalocyanine anchored on electrospun polystyrene polymer fiber
- Zugle, Ruphino, Antunes, Edith M, Khene, Samson M, Nyokong, Tebello
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
- Authors: Zugle, Ruphino , Antunes, Edith M , Khene, Samson M , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/245787 , vital:51405 , xlink:href="https://doi.org/10.1016/j.poly.2011.11.005"
- Description: An electrospun polystyrene (PS) fiber incorporating tetraphenoxy phthalocyanine complex of lutetium (LuTPPc/PS) as a photosensitizer was applied for the degradation of 4-chlorophenol in aqueous solution in the presence of visible light. The photocatalytic activity of the LuTPPc in the fiber was compared to that of zinc phthalocyanine (ZnPc) incorporated into the PS fiber, and the former showed higher activity. UV–Vis spectral changes of sample solutions indicated transformation of the analyte with first order kinetics and half-lives that are within one and half hours for LuTPPc/PS. Products identified from the spectral changes and gas chromatography were benzoquinone, hydroquinone and 4,4′-dihydroxydiphenol suggesting that the photodegradation of 4-chlorophenol was through both Types I and II mechanisms.
- Full Text:
- Date Issued: 2012
Synthesis, electrochemical characterization of tetra-and octa-substituted dodecyl-mercapto tin phthalocyanines in solution and as self-assembled monolayers
- Khene, Samson M, Geraldo, Daniela A, Togo, Chamunorwa A, Limson, Janice L, Nyokong, Tebello
- Authors: Khene, Samson M , Geraldo, Daniela A , Togo, Chamunorwa A , Limson, Janice L , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264541 , vital:53743 , xlink:href="https://doi.org/10.1016/j.electacta.2008.08.018"
- Description: Non-peripherally (α) tetra- (9) and octa-(7) substituted dodecyl-mercapto tin(IV) phthalocyanines were synthesized and their electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for 7 and 9, the former shows two ring oxidations, while the latter shows only one ring-based oxidation. The adsorption kinetics of (7) and (9) on gold electrode were investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy (ΔGads) of the SAMs were evaluated based on the Frumkin isotherm.
- Full Text:
- Date Issued: 2008
- Authors: Khene, Samson M , Geraldo, Daniela A , Togo, Chamunorwa A , Limson, Janice L , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/264541 , vital:53743 , xlink:href="https://doi.org/10.1016/j.electacta.2008.08.018"
- Description: Non-peripherally (α) tetra- (9) and octa-(7) substituted dodecyl-mercapto tin(IV) phthalocyanines were synthesized and their electrochemical behavior studied. Cyclic voltammetry and spectroelectrochemistry show ring-based reductions for 7 and 9, the former shows two ring oxidations, while the latter shows only one ring-based oxidation. The adsorption kinetics of (7) and (9) on gold electrode were investigated by electrochemical impedance spectroscopy (EIS). The equilibrium constant (K) for the adsorption and the Gibbs free energy (ΔGads) of the SAMs were evaluated based on the Frumkin isotherm.
- Full Text:
- Date Issued: 2008
Synthesis, photophysical and nonlinear optical behavior of neodymium based trisphthalocyanine
- Sekhosana, Kutloana E, Amuhaya, Edith K, Khene, Samson M, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Khene, Samson M , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241412 , vital:50937 , xlink:href="https://doi.org/10.1016/j.ica.2014.11.029"
- Description: Tris-{1(4),8(11),15(18),22(25)-tetra(4-tertbutylphenoxy) phthalocyaninato} dineodymium (III) was synthesised and its nonlinear optical and fluorescence behavior was studied. Low fluorescence quantum yield (ФF = 0.03) was obtained with a fluorescence lifetime τF = 4.31 ns for this complex. Nonlinear optical parameters for the complex were determined using the Z-scan technique and the values of Im[χ(3)] and γ were of the order of 10−10 and 10−28 esu, respectively. Square wave voltammetry revealed three reduction and two oxidation couples for the complex.
- Full Text:
- Date Issued: 2015
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith K , Khene, Samson M , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241412 , vital:50937 , xlink:href="https://doi.org/10.1016/j.ica.2014.11.029"
- Description: Tris-{1(4),8(11),15(18),22(25)-tetra(4-tertbutylphenoxy) phthalocyaninato} dineodymium (III) was synthesised and its nonlinear optical and fluorescence behavior was studied. Low fluorescence quantum yield (ФF = 0.03) was obtained with a fluorescence lifetime τF = 4.31 ns for this complex. Nonlinear optical parameters for the complex were determined using the Z-scan technique and the values of Im[χ(3)] and γ were of the order of 10−10 and 10−28 esu, respectively. Square wave voltammetry revealed three reduction and two oxidation couples for the complex.
- Full Text:
- Date Issued: 2015
Nonlinear optical properties of metal free and nickel binuclear phthalocyanines
- Kabwe, Kapambwe P, Louzada, Marcel, Britton, Jonathan, Olomola, Temitope O, Nyokong, Tebello, Khene, Samson M
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola, Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
- Full Text:
- Date Issued: 2019
- Authors: Kabwe, Kapambwe P , Louzada, Marcel , Britton, Jonathan , Olomola, Temitope O , Nyokong, Tebello , Khene, Samson M
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186846 , vital:44539 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.05.003"
- Description: This work employs the open and closed Z-scan aperture technique to comparatively study the nonlinear optical (NLO) properties of nickel and metal free 4-tert-butylphenoxy phthalocyanine, biphenyl bridged bis-4-tert-butylphenoxy phthalocyanine and naphthalene bridged bis-4-tert-butylphenoxy phthalocyanine. Density functional theory (DFT) calculations of dipolar and octupolar ( J=1 and J=3) contribution were determined theoretically from hyper-Rayleigh scattering (HRS) response ( HRS) values.
- Full Text:
- Date Issued: 2019
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