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
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
The effect of the cobalt and manganese central metal ions on the nonlinear optical properties of tetra (4-propargyloxyphenoxy) phthalocyanines
- Mwanza, Daniel, Louzada, Marcel, Britton, Jonathan, Sekhosana, Kutloano E, Khene, Samson M, Nyokong, Tebello, Mashazi, Philani N
- Authors: Mwanza, Daniel , Louzada, Marcel , Britton, Jonathan , Sekhosana, Kutloano E , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233357 , vital:50083 , xlink:href="https://doi.org/10.1039/C8NJ00748A"
- Description: The metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (Mn(OAc)TPrOPhOPc) tetra propargyloxyphenoxy phthalocyanines were evaluated for their potential as optical limiting materials. The effect of the substituents and the central metal ions on the nonlinear optical properties was evaluated. The metal-free phthalocyanine exhibited better nonlinear optical properties when compared to the cobalt and manganese complexes owing to the metal ions quenching the excited state due to their half-filled d-orbitals. The nonlinear absorption coefficient (βeff, ×10−5 m MW−1) followed the trend of H2TPrOPhOPc > CoTPrOPhOPc > Mn(OAc)TPrOPhOPc. The values βeff (×10−5 m MW−1) using 532 nm Nd:YAG (560 nm monochromatic Ekspla) laser sources were 23.5 > 14.3 > 9.20 (14.4). The second-order nonlinear coefficient obtained using density functional theory calculations, the theoretical hyper-Rayleigh scattering (βHRS, ×10−28 esu), showed the decreasing trend for H2TPrOPhOPc (2.28) > CoTPrOPhOPc (2.10) > Mn(OAc)TPrOPhOPc (1.86). The 4-(propargyloxy)phenoxy substituents enhanced the optical limiting properties of the synthesized phthalocyanines.
- Full Text:
- Date Issued: 2018
- Authors: Mwanza, Daniel , Louzada, Marcel , Britton, Jonathan , Sekhosana, Kutloano E , Khene, Samson M , Nyokong, Tebello , Mashazi, Philani N
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233357 , vital:50083 , xlink:href="https://doi.org/10.1039/C8NJ00748A"
- Description: The metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (Mn(OAc)TPrOPhOPc) tetra propargyloxyphenoxy phthalocyanines were evaluated for their potential as optical limiting materials. The effect of the substituents and the central metal ions on the nonlinear optical properties was evaluated. The metal-free phthalocyanine exhibited better nonlinear optical properties when compared to the cobalt and manganese complexes owing to the metal ions quenching the excited state due to their half-filled d-orbitals. The nonlinear absorption coefficient (βeff, ×10−5 m MW−1) followed the trend of H2TPrOPhOPc > CoTPrOPhOPc > Mn(OAc)TPrOPhOPc. The values βeff (×10−5 m MW−1) using 532 nm Nd:YAG (560 nm monochromatic Ekspla) laser sources were 23.5 > 14.3 > 9.20 (14.4). The second-order nonlinear coefficient obtained using density functional theory calculations, the theoretical hyper-Rayleigh scattering (βHRS, ×10−28 esu), showed the decreasing trend for H2TPrOPhOPc (2.28) > CoTPrOPhOPc (2.10) > Mn(OAc)TPrOPhOPc (1.86). The 4-(propargyloxy)phenoxy substituents enhanced the optical limiting properties of the synthesized phthalocyanines.
- Full Text:
- Date Issued: 2018
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
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
Solvent effect on the third-order nonlinear optical properties of α-and β-tertbutyl phenoxy-substituted tin (IV) chloride phthalocyanines
- Louzada, Marcel, Britton, Jonathan, Nyokong, Tebello, Khene, Samson M
- Authors: Louzada, Marcel , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188910 , vital:44797 , xlink:href="https://doi.org/10.1021/acs.jpca.7b07349"
- Description: This paper investigates the third-order nonlinear optical properties of 4α-(4-tert-butylphenoxy) phthalocyaninato dichlorotin(IV) (α-SnOtBpPc) and 4β-(4-tert-butylphenoxy) phthalocyaninato dichlorotin(IV) (β-SnOtBpPc) in different organic solvents. The third-order susceptibilities of α-SnOtBpPc and βSnOtBpPc are reported in different solvents, using Z-scan techniques with 10 ns laser pulses at 532 nm. Their nonlinear absorption coefficient and absorption cross sections were also determined. The molecular imaginary components of the secondorder hyperpolarizability Im[γ] of α-SnOtBpPc and β-SnOtBpPc were found to be 2.60 × 10−31 and 2.94 × 10−31 esu (tetrahydrofuran), 2.12 × 10−31 and 2.54 × 10−31 esu (chloroform), 3.06 × 10−31 and 2.54 × 10−31 esu (dichloromethane), and 1.27 × 10−31 and 1.50 × 10−31 esu (toluene), respectively. This study found that substitution at the α position has an effect of lowering the two-photon (2PA) cross section value for α-SnOtBpPc compared to that for β-SnOtBpPc, with values of 64.30 and 456.65 GM, respectively. The large 2PA cross section observed in β-SnOtBpPc is attributed to the decreased energy difference between the virtual state and the LUMO.
- Full Text:
- Date Issued: 2017
- Authors: Louzada, Marcel , Britton, Jonathan , Nyokong, Tebello , Khene, Samson M
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188910 , vital:44797 , xlink:href="https://doi.org/10.1021/acs.jpca.7b07349"
- Description: This paper investigates the third-order nonlinear optical properties of 4α-(4-tert-butylphenoxy) phthalocyaninato dichlorotin(IV) (α-SnOtBpPc) and 4β-(4-tert-butylphenoxy) phthalocyaninato dichlorotin(IV) (β-SnOtBpPc) in different organic solvents. The third-order susceptibilities of α-SnOtBpPc and βSnOtBpPc are reported in different solvents, using Z-scan techniques with 10 ns laser pulses at 532 nm. Their nonlinear absorption coefficient and absorption cross sections were also determined. The molecular imaginary components of the secondorder hyperpolarizability Im[γ] of α-SnOtBpPc and β-SnOtBpPc were found to be 2.60 × 10−31 and 2.94 × 10−31 esu (tetrahydrofuran), 2.12 × 10−31 and 2.54 × 10−31 esu (chloroform), 3.06 × 10−31 and 2.54 × 10−31 esu (dichloromethane), and 1.27 × 10−31 and 1.50 × 10−31 esu (toluene), respectively. This study found that substitution at the α position has an effect of lowering the two-photon (2PA) cross section value for α-SnOtBpPc compared to that for β-SnOtBpPc, with values of 64.30 and 456.65 GM, respectively. The large 2PA cross section observed in β-SnOtBpPc is attributed to the decreased energy difference between the virtual state and the LUMO.
- Full Text:
- Date Issued: 2017
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