Electrochemical and electrocatalytic properties of α-substituted manganese and titanium phthalocyanines
- Authors: Nombona, Nolwazi , Tau, Prudence , Sehlotho, Nthapo , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268587 , vital:54212 , xlink:href="https://doi.org/10.1016/j.electacta.2007.11.046"
- Description: This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.
- Full Text:
- Date Issued: 2008
Comparative photocatalytic efficiency of oxotitanium (IV) phthalocyanines for the oxidation of 1-hexene
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271193 , vital:54520 , xlink:href="https://doi.org/10.1016/j.molcata.2007.04.005"
- Description: The comparative photocatalytic activities of aryloxy and arylthio tetrasubstituted oxotitanium(IV) phthalocyanine complexes for the oxidation of 1-hexene in DCM are reported for the first time. The singlet oxygen quantum yield, photostability and photocatalytic properties are investigated. The catalysts effectively catalyse 1-hexene to 1,2-epoxyhexane and 1-hexen-3-ol as major and minor products respectively. The photooxidation products are formed via two reaction mechanisms, namely via singlet oxygen (Type II) and radical (Type I) reaction pathways. These are also dependent on the singlet oxygen quantum yields and photostabilities of the phthalocyanines. Complex 1a that is peripherally substituted with phenoxy groups exhibited the best activity in terms of overall performance.
- Full Text:
- Date Issued: 2007
Electrocatalytic activity of arylthio tetra-substituted oxotitanium (IV) phthalocyanines towards the oxidation of nitrite
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281234 , vital:55704 , xlink:href="https://doi.org/10.1016/j.electacta.2006.12.059"
- Description: This paper investigates the catalytic activities of arylthio substituted oxotitanium phthalocyanine (OTiPc) complexes that are immobilized on the glassy carbon electrode by electropolymerization, towards the oxidation of nitrite. The complexes are peripherally and non-peripherally substituted with phenylthio and benzylthio groups, namely 1a, 1b, 2a and 2b. All the modified electrodes exhibited improved electrocatalytic oxidation of nitrite than the unmodified electrodes by a two-electron mechanism producing nitrate ions. Catalytic currents are enhanced and nitrite overpotential reduced to ∼0.60 V. Kinetic parameters are determined for all complexes and a mechanism is proposed.
- Full Text:
- Date Issued: 2007
Electrocatalytic oxidation of nitrite by tetra-substituted oxotitanium (IV) phthalocyanines adsorbed or polymerised on glassy carbon electrode
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268762 , vital:54230 , xlink:href="https://doi.org/10.1016/j.jelechem.2007.07.019"
- Description: Comparative electrocatalytic oxidation of nitrite by tetra aryloxy-substituted oxotitanium(IV) and tetraamino phthalocyanine complexes is investigated in this work. The aryloxy complexes are substituted at the peripheral (4) and non-peripheral (5) positions with phenoxy (complexes a), 4-tert-butylphenoxy (complexes b), benzyloxy (complexes c) and 4-(benzyloxy)phenoxy (complexes d) groups. The glassy carbon electrode was employed and modified with the tetra aryloxy-substituted titanium phthalocyanine complexes (4 and 5) by adsorption, and with titanium tetraamino phthalocyanine (TiTAPc) by polymerisation. All complexes reduced the overpotential of the nitrite electrooxidation as well as enhanced the catalytic current by a 2 electron process.
- Full Text:
- Date Issued: 2007
Spectroscopic characterisation and interactions of sulfonated titanium and tantalum phthalocyanines with methyl viologen
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283129 , vital:55913 , xlink:href="https://doi.org/10.1016/j.ica.2006.12.035"
- Description: Sulfonated OTiPc(S)n and (Cl3)TaPc(S)n complexes are prepared and characterised by spectroscopic methods in DMSO, methanol and PBS 7.4. The dominant sulfonated species was the disulfophthalocyanine. OTiPc(S)n is highly aggregated in PBS 7.4 solution and tends to partially monomerise, on addition of Triton X-100, while (Cl3)TaPc(S)n showed broadened spectra in all solvents and was not affected by Triton X-100. The absorption and excitation spectra of OTiPc(S)n are similar and are mirror images of their emission spectra in DMSO, but differ in PBS and methanol. The fluorescence quantum yields (ϕF) and lifetimes (τF) were larger in DMSO than in methanol. In PBS 7.4, however, the ϕF and τF values were significantly smaller for OTiPc(S)n, which is typical of aggregated species. Gradual addition of the electron-acceptor MV2+ to solutions of MPc(S)n complexes resulted in the fluorescence quenching of complexes with higher quenching observed for OTiPc(S)n. The interaction of the MPc(S)n complexes with MV2+, and hence the stoichiometry and association constants are evaluated by means of Job method.
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- Date Issued: 2007
Synthesis and electrochemical properties of purple manganese (III) and red titanium (IV) phthalocyanine complexes octa-substituted at non-peripheral positions with pentylthio groups
- Authors: Mbambisa, Gcineka , Tau, Prudence , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271252 , vital:54525 , xlink:href="https://doi.org/10.1016/j.poly.2007.08.007"
- Description: The synthesis and electrochemical characterisation of octapentylthiophthalocyaninato manganese (III) acetate (4) and octapentylthiophthalocyaninato titanium (IV) oxide (5) complexes are reported. The complexes have an unusual purple (4) and red (5) colouration since the Q-band is shifted to the near infrared region with Q-band maxima at 893 nm and 808 nm in dichloromethane for 4 and 5, respectively. The structures of the complexes were confirmed by elemental analysis and interpretation of their spectroscopic data, including 2D NMR. The cyclic voltammetry (CV) of the Mn complex (4) showed four quasi reversible couples. The reduction processes are attributed to MnIIIPc−2/MnIIPc−2 and MnIIPc−2/MnIIPc−3 and the oxidation processes to MnIVPc−2/MnIIIPc−2 and MnIVPc−1/MnIVPc−2. The processes were confirmed by spectroelectrochemistry. A well-defined spectrum of the rare MnIVPc−2 species is reported. The CV of the Ti complex (5) showed two well-resolved reduction processes due to TiIVPc−2/TiIIIPc−2 and TiIIIPc−2/TiIIPc−2. However, oxidation processes of the complex revealed adsorption behaviour and resulted in decomposition on electrolysis using spectroelectrochemistry.
- Full Text:
- Date Issued: 2007
Synthesis and electrochemical characterisation of α-and β-tetra-substituted oxo (phthalocyaninato) titanium (IV) complexes
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283869 , vital:55998 , xlink:href="https://doi.org/10.1016/j.poly.2005.11.025"
- Description: The synthesis, spectroscopic and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetraphenoxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)-(tetra-tert-butylphenoxyphthalocyaninato)titanium(IV) oxide (5b); 2,(3)-(tetraphenoxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-(tetra-tert-butylphenoxyphthalocyaninato)titanium(IV) oxide (6b). Complexes 5a and 5b are substituted at the non-peripheral (α) positions, whereas complexes 6a and 6b are substituted at the peripheral (β) positions. Cyclic voltammograms of all four complexes are similar, with three reversible reduction couples and three quasi-reversible to irreversible oxidations. The first two reductions are two-electron processes, confirmed by spectroelectrochemistry to be due to TiIVPc−2/TiIIPc−3 and TiIIPc−2/TiIPc−3 redox processes. Spectroelectrochemistry showed that upon oxidation, the molecule decomposes. Oxidation is expected to occur at the ring. Chronocoulometry confirmed two electron transfer at the first and second reduction steps; and a one electron transfer at the third reduction.
- Full Text:
- Date Issued: 2006
Synthesis and photophysical properties of octa-substituted phthalocyaninato oxotitanium (IV) derivatives
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283881 , vital:55999 , xlink:href="https://doi.org/10.1142/S1088424606000399"
- Description: The synthesis, spectral and photophysical properties including fluorescence quenching of the following octa-substituted oxotitanium phthalocyanines are reported: 2,3,9,10,16,17,23,24-octaphenoxyphthalocyaninato titanium(IV) oxide, 2,3,9,10,16,17,23,24-[octakis(4-t-butylphenoxyphthalocyaninato)]titanium(IV) oxide, 2,3,9,10,16,17,23,24-{octakis[(4-benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide and 2,3,9,10,16,17,23,24-octaphenylthiophthalocyaninato titanium(IV) oxide. The complexes are characterized by 1H NMR, IR and UV-vis spectroscopies. Their photophysical properties are presented where moderate fluorescence quantum yields (0.14-0.19) and lifetimes were determined. Varied triplet quantum yields were obtained and the triplet lifetimes (40-100 μs) were short.
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- Date Issued: 2006
Unique electrochemical behavior of tantalum (V) phthalocyanine
- Authors: Tau, Prudence , Nyokong, Tebello
- Date: 2006
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/286139 , vital:56243 , xlink:href="https://doi.org/10.1142/S1088424606000090"
- Description: The electrochemical and spectroscopic behavior of tantalum(V) phthalocyanine are presented. The NMR spectra is consistent with the lack of symmetry of the complex. Cyclic (CV) and square wave (SWV) voltammetries, and spectroelectrochemistry, were employed in the study of the complex. Two one-electron reductions and a simultaneous 4-electron reduction were observed. Reduction occurs first at the metal to form a Ta(IV) species, followed by ring based processes.
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- Date Issued: 2006
Influence of cyclodextrins on the fluorescence, photostability and singlet oxygen quantum yields of zinc phthalocyanine and naphthalocyanine complexes
- Authors: Tau, Prudence , Ogunsipe, Abimbola O , Maree, Suzanne , Maree, M David , Nyokong, Tebello
- Date: 2003
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304775 , vital:58488 , xlink:href="https://doi.org/10.1142/S1088424603000562"
- Description: The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine (ZnPc) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine (ZnNPc) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.
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- Date Issued: 2003