Characterization of self-assembled monolayers of iron and cobalt octaalkylthiosubstituted phthalocyanines and their use in nitrite electrocatalytic oxidation
- Authors: Matemadombo, Fungisai , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271182 , vital:54519 , xlink:href="https://doi.org/10.1016/j.electacta.2007.05.002"
- Description: Cobalt and iron phenylthiosubstituted phthalocyanines have been deposited on Au electrode surfaces through the self-assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric and impedance techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of nitrite. The electrocatalytic parameters of the cobalt and iron phenylthiosubstituted phthalocyanines deposited on Au electrodes in nitrite solution were studied. Nitrite overpotentials which are lower than ever reported were obtained in this work for the iron phenylthiosubstituted phthalocyanines with very high stability.
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- Date Issued: 2007
Cobalt Phthalocyanine Molecular Electrode for the Electrochemical Investigation of the Release of Glutathione upon Copper-Catalyzed Decomposition of S-Nitrosoglutathione
- Authors: Sehlotho, Nthapo , Griveau, Sophie , Nyokong, Tebello , Bedioui, Fethi
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281201 , vital:55701 , xlink:href="https://doi.org/10.1002/elan.200603656"
- Description: Decomposition of S-nitrosoglutathione (GSNO) in phosphate buffer solution at physiological pH 7.4 in the presence of cuprous ion as a catalyst and sodium borohydride as a reducing agent is analyzed by observing the transient apparition of reduced glutathione GSH through its electrooxidation. Transient formation of GSH, upon decomposition of 1 mM GSNO in presence of 0.025 mM Cu(NO3)2 and 1 mM NaBH4 was detected by using an ordinary pyrolytic graphite electrode modified with an adsorbed monolayer of cobalt phthalocyanine at 0 V vs. SCE.
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- Date Issued: 2007
Comparative electrooxidation of nitrite by electrodeposited Co (II), Fe (II) and Mn (III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines on gold electrodes
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281212 , vital:55702 , xlink:href="https://doi.org/10.1016/j.aca.2007.01.031"
- Description: This work reports on the electrooxidation of nitrite using Co(II), Fe(II) and Mn(III) tetrakis (benzylmercapto) and tetrakis (dodecylmercapto) phthalocyanines electrodeposited onto a gold electrode. Good catalytic activity (in terms of lowering overpotential) was obtained for these molecules when compared to previously reported MPc catalysts. The catalytic current was found to vary linearly with nitrite concentration in the range employed in this work (0.1–1 mM) and high sensitivities ranging from 6.9 to 9.9 μA mM−1 were observed for all the modified electrodes.
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- Date Issued: 2007
Comparative electrooxidation of sulphite by self-assembled monolayers (SAMs) of Co (II), Fe (II), Ni (II) and Mn (III) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281223 , vital:55703 , xlink:href="https://doi.org/10.1016/j.talanta.2006.11.042"
- Description: This work reports on the use of Co(II), Fe(II), Mn(III) and Ni(II) tetrakis benzylmercapto and dodecylmercapto phthalocyanine complexes for gold electrode modification for electrooxidation of sulphite ions. The complexes were successfully used to modify gold electrodes by self-assembled monolayer (SAM) technique. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, underpotential deposition (UPD) of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. All the modified electrodes showed improved catalytic activities than the unmodified gold electrode towards sulphite ion electrooxidation with all the modified electrodes exhibiting high resistance to electrode surface passivation. Better catalytic performance were obtained for the CoPcs, FePcs and MnPcs which have metal based redox processes within the range of the sulphite electrooxidation peak, while the NiPcs which did not show metal based redox reaction performed less. The catalytic current was found to be linear with sulphite ion concentration in the concentration range employed in this work (0.1–1 mM) and sensitivities ranging from 1.68 to 2.96 μA/mM were observed for all the modified electrodes. Mechanisms of the catalytic oxidation of sulphite ions are proposed.
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- Date Issued: 2007
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.
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- Date Issued: 2007
Critical assessment of the quartz crystal microbalance with dissipation as an analytical tool for biosensor development and fundamental studies
- Authors: Fogel, Ronen , Mashazi, Philani N , Nyokong, Tebello , Limson, Janice L
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271204 , vital:54521 , xlink:href="https://doi.org/10.1016/j.bios.2007.03.012"
- Description: One of the challenges in electrochemical biosensor design is gaining a fundamental knowledge of the processes underlying immobilisation of the molecules onto the electrode surface. This is of particular importance in biocomposite sensors where concerns have arisen as to the nature of the interaction between the biological and synthetic molecules immobilised. We examined the use of the Quartz Crystal Microbalance with Dissipation (QCM-D) as a tool for fundamental analyses of a model sensor constructed by the immobilisation of cobalt(II) phthalocyanine (TCACoPc) and glucose oxidase (GOx) onto a gold-quartz electrode (electrode surface) for the enhanced detection of glucose. The model sensor was constructed in aqueous phase and covalently linked the gold surface to the TCACoPc, and the TCACoPc to the GOx, using the QCM-D. The aqueous metallophthalocyanine (MPc) formed a multi-layer over the surface of the electrode, which could be removed to leave a monolayer with a mass loading that compared favourably to the theoretical value expected. Analysis of frequency and dissipation plots indicated covalent attachment of glucose oxidase onto the metallophthalocyanine layer. The amount of GOx bound using the model system compared favourably to calculations derived from the maximal amperometric functioning of the electrochemical sensor (examined in previously-published literature, Mashazi, P.N., Ozoemena, K.I., Nyokong, T., 2006. Electrochim. Acta 52, 177–186), but not to theoretical values derived from dimensions of GOx as established by crystallography. The strength of the binding of the GOx film with the TCACoPc layer was tested by using 2% SDS as a denaturant/surfactant, and the GOx film was not found to be significantly affected by exposure to this. This paper thus showed that QCM-D can be used in order to model essential processes and interactions that dictate the functional parameters of a biosensor.
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- Date Issued: 2007
Effects of substituents on the photochemical and photophysical properties of main group metal phthalocyanines
- Authors: Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6581 , http://hdl.handle.net/10962/d1004146
- Description: The review focuses on the photochemical (singlet oxygen and photobleaching quantum yields) and photophysical (triplet quantum yields and lifetimes and fluorescence lifetimes) properties of metallophthalocyanine complexes containing main group metals (Zn, Al, Ge, Si, Sn, Ga and In) and some unmetallated phthalocyanine complexes. Five tables containing photophysical and photochemical data for sulfonated phthalocyanines, tetra-, octa-substituted and unsubstituted phthalocyanines in a variety of solvents, are included in the review.
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- Date Issued: 2007
Electroanalysis of thiocyanate using a novel glassy carbon electrode modified by aryl radicals and cobalt tetracarboxyphthalocyanine
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268750 , vital:54228 , xlink:href="https://doi.org/10.1016/j.electacta.2007.06.064"
- Description: Electrochemical grafting of 4-nitrobenzenediazonium tetrafluoroborate onto a glassy carbon electrode (GCE) results in the formation of a nitrophenyl radical, which reacts with the surface to form a covalent bond (grafting) and results in a nitrophenyl modified electrode. The nitro group is electrochemically reduced to a NH2 group. Cobalt tetracarboxyphthalocyanine (CoTCPc) complex is then attached to the NH2 group using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS) as coupling agents. The new CoTCPc modified electrode was characterized using cyclic voltammetry and then employed for the catalytic oxidation of thiocyanate.
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- 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.
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- Date Issued: 2007
Electrocatalytic oxidation of chlorophenols by electropolymerised nickel (II) tetrakis benzylmercapto and dodecylmercapto metallophthalocyanines complexes on gold electrodes
- Authors: Agboola, Bolade , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281247 , vital:55705 , xlink:href="https://doi.org/10.1016/j.electacta.2007.02.017"
- Description: This work reports on the use of nickel(II) tetrakis benzylmercapto (NiTBMPc) and dodecylmercapto (NiTDMPc) metallophthalocyanine complexes films on gold electrodes for the electrochemical oxidation of 4-chlorophenol (4-CP) and 2,4,5-trichlorophenol (TCP). Both NiTBMPc and NiTDMPc complexes were successfully deposited on gold electrodes by electropolymerisation. The films were electro-transformed in aqueous 0.1 M NaOH solution to the ‘O–Ni–O oxo’ bridged form. For both complexes, films with different thickness were prepared and characterised by electrochemical impedance and UV–vis (on indium tin oxide) spectroscopies and the results showed typical behaviour for modified electrodes with increasing charge transfer resistance values (Rp) with polymer thickness. The poly-Ni(OH)NiPcs showed better catalytic activity than their poly-NiPcs counterparts.
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- 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.
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- Date Issued: 2007
Electrochemical and photophysical characterization of non-peripherally-octaalkyl substituted dichlorotin (IV) phthalocyanine and tetrabenzotriazaporphyrin compounds
- 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.
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- Date Issued: 2007
Electrochemical characterisation of tetra- and octa-substituted oxo(phthalocyaninato)titanium(IV) complexes
- Authors: Tau, Prudence Lerato , Nyokong, Tebello
- Date: 2007
- Language: English
- Type: Article
- Identifier: vital:6598 , http://hdl.handle.net/10962/d1004347
- Description: The synthesis and electrochemical characterisation of the following oxotitanium tetra-substituted phthalocyanines are reported: 1,(4)-(tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (5a); 1,(4)- {tetrakis[4-(benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (5b); 2,(3)- (tetrabenzyloxyphthalocyaninato)titanium(IV) oxide (6a) and 2,(3)-{tetrakis[4- (benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide (6b). The electrochemical characterisation of complexes octa-substituted with 4-(benzyloxy)phenoxy (9b), phenoxy (9c) and tert -butylphenoxy (9d) groups is also reported. The cyclic voltammograms of the complexes exhibit reversible couples I–III and couple IV is quasi-reversible for complexes 5a, 5b, 6a and 6b. The first two reductions are metal-based processes, confirmed by spectroelectrochemistry to be due to Ti IV Pc 2 − /Ti III Pc 2 − and Ti III Pc 2 − /Ti II Pc 2 − redox processes and the last two reductions are ring-based processes due to Ti II Pc 2 − /Ti II Pc 3 − and Ti II Pc 3 − /Ti II Pc 4 − . Chronocoulometry confirmed a one-electron transfer at each reduction step. The electrochemistry of the above complexes is also compared to the previously reported 5c, 5d, 6c and 6d.
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- Date Issued: 2007
Excited state dynamics of zinc and aluminum phthalocyanine carboxylates
- Authors: Idowu, Mopelola , Ogunsipe, Abimbola , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/271228 , vital:54523 , xlink:href="https://doi.org/10.1016/j.saa.2007.01.025"
- Description: Photophysical parameters for zinc and aluminium tetracarboxylphthalocyanines (ZnTCPc and AlTCPc, respectively) and their octacarboxy substituted counterparts (ZnOCPc and AlOCPc) were studied. Data for the fluorescence quenching of the complexes by benzoquinone (BQ) were treated using the Stern–Volmer analysis, and the quenching was found to follow a diffusion-controlled (dynamic) bimolecular mechanism. Theoretical values of bimolecular rate constant for complex-BQ interactions were determined using the Stokes–Einstein–Smoluchowski model; and the values, together with the Stern–Volmer quenching constants were used in calculating the fluorescence lifetimes of the complexes. The thermodynamics of the MPc-BQ interaction, in terms of solvent reorientation energy is also discussed.
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- Date Issued: 2007
Immobilization of tetra-amine substituted metallophthalocyanines at gold surfaces modified with mercaptopropionic acid or DTSP-SAMs
- Authors: Matemadombo, Fungisai , Westbroek, Philippe , Nyokong, Tebello , Ozoemena, Kenneth , De Clerck, Karen , Kiekens, Paul
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283924 , vital:56003 , xlink:href="https://doi.org/10.1016/j.electacta.2006.08.027"
- Description: This paper shows that amine substituted cobalt phthalocyanine (CoTAPc) can be deposited on gold surfaces by using an interconnecting layer of a self-assembled monolayer (SAM) of mercaptopropionic acid or Lomant's reagent (dithiobis(N-succinimidyl propionate) (DTSP)). In both cases the new bond formed is obtained by the creation of an amide. The layers were characterized by electrochemistry and showed high coverage fractions (near 100%). Reductive and oxidative desorption of the SAMs limit the useful potential window from −0.6 to +0.5 V versus Ag|AgCl. The SAM-CoTAPc layers show electrocatalytic activities towards oxygen reduction through the Co(I) central metal ion. The amount of CoTAPc molecules deposited (obtained from the Co central metal ion activity in nitrogen purged solutions) revealed that the CoTAPc molecules are bonded in a perpendicular manner at the surface. Taking into account a surface of 200 Å2 for a flatly bonded MPc, this should result in a four times less amount of deposited CoTAPc compared to the experimental value obtained. Both methods showed good results and promising long-term stability and will be interesting tools for further research in surface modification and sensor development.
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- Date Issued: 2007
Insights into the surface and redox properties of single-walled carbon nanotube—cobalt (II) tetra-aminophthalocyanine self-assembled on gold electrode
- Authors: Ozoemena, Kenneth I , Nyokong, Tebello , Nkosi, Duduzile , Chambrier, Isabelle , Cook, Michael J
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281258 , vital:55707 , xlink:href="https://doi.org/10.1016/j.electacta.2006.11.039"
- Description: This paper describes for the first time the electrochemical properties of redox-active self-assembled films of single-walled carbon nanotubes (SWCNTs) coordinated to cobalt(II)tetra-aminophthalocyanine (CoTAPc) by sequential self-assembly onto a preformed aminoethanethiol (AET) self-assembled monolayer (SAM) on a gold electrode. Both redox-active SAMs (Au-AET-SWCNT and Au-AET-SWCNT-CoTAPc) exhibited reversible electrochemistry in aqueous (phosphate buffer) solution. X-ray photoelectron spectroscopy (XPS) confirmed the appearance on the gold surface of the various elements found on the SAMs. Atomic force microscopy (AFM) images prove, corroborating the estimated electrochemical surface concentrations, that these SAMs lie normal to the gold surface. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)6]3−/4− as a redox probe revealed that the Au-AET-SWCNT-CoTAPc showed much lower (∼10 times) electron-transfer resistance (Ret) and much higher (∼10 times) apparent electron-transfer rate constant (kapp) compared to the Au-AET-SWCNT SAM. Interestingly, a preliminary electrocatalytic investigation showed that both SAMs exhibit comparable electrocatalytic responses towards the detection of dopamine in pH 7.4 phosphate buffer solutions (PBS). The electrochemical studies (cyclic voltammetry (CV) and EIS) prove that SWCNT greatly improves the electronic communication between CoTAPc and the Au electrode surface.
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- Date Issued: 2007
Microwave synthesis and photophysics of new tetrasulfonated tin (II) macrocycles
- Authors: Khene, Samson , Ogunsipe, Abimbola , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281269 , vital:55708 , xlink:href="https://doi.org/10.1142/S108842460700014X"
- Description: This work reports on the microwave synthesis of tetrasulfonated tin phthalocyanine and tetrasulfonated tin α,β,γ-tetrabenzcorrole. The latter was only formed at low ratios (more than 1:8) of 4-sulfophthalic acid to urea. Both complexes are aggregated in aqueous media, but can be partly or fully disaggregated by the addition of Triton X-100. The α,β,γ-tetrabenzcorrole complex has lower triplet life times and yields, while the binding constant and quenching (of bovine serum albumin) constant are lower for α,β,γ-tetrabenzcorrole compared to tetrasulfonated tin phthalocyanine.
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- Date Issued: 2007
Novel gallium (III) phthalocyanine derivatives–Synthesis, photophysics and photochemistry
- Authors: Chauke, Vongani , Ogunsipe, Abimbola , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/283118 , vital:55912 , xlink:href="https://doi.org/10.1016/j.poly.2007.01.016"
- Description: The syntheses of gallium(III) chloride phthalocyanine {(Cl)GaPc}, octaphenoxyphthalocyaninato gallium(III) chloride {(Cl)GaOPPc} and octakis(4-tert-butylphenoxy)phthalocyaninato gallium(III) chloride {(Cl)GaOTBPPc}; as well as their photophysical and photochemical parameters are hereby presented. Fluorescence quantum yields do not vary much among the three metallophthalocyanines (MPcs); therefore it was concluded that the effect of the substituents is not significant amongst (Cl)GaPc, (Cl)GaOPPc and (Cl)GaOTBPPc. Solvents effects, however, had an effect on the results. Triplet quantum yields were found to be lower in DMSO than in DMF and toluene. The rate constants for fluorescence, intersystem crossing and internal conversion as well as fluorescence and triplet lifetimes are reported. We have also reported photodegradation and singlet oxygen quantum yields. There was no clear correlation between the later parameters. It was, however, established that the three MPcs were stable.
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- Date Issued: 2007
Photocatalysis of 4-nitrophenol using zinc phthalocyanine complexes
- Authors: Marais, Eloïse A , Klein, Rosalyn , Antunes, Edith M , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/281286 , vital:55709 , xlink:href="https://doi.org/10.1016/j.molcata.2006.07.055"
- Description: Photodegradation of 4-nitrophenol (4-Np) in the presence of zinc tetrasulfophthalocyanine (ZnPcS4), zinc octacarboxyphthalocyanine (ZnPc(COOH)8) and a sulfonated ZnPc containing a mixture of differently sulfonated derivatives (ZnPcSmix), as photocatalysts is reported. ZnPcSmix is the most effective catalyst in terms of a high quantum yield for 4-Np degradation and the stability of the catalyst. However ZnPc(COOH)8 degrades readily during the catalysis, but it has a higher quantum yield (Φ4-Np) for 4-Np degradation than the rest of the complexes. The Φ4-Np values were closely related to the singlet oxygen quantum yields ΦΔ and hence aggregation. The rate constants for the reaction with 4-Np were kr = 0.67 × 106 mol−1 dm3 s−1 for ZnPcSmix and 2.8 × 108 mol−1 dm3 s−1 for ZnPc(COOH)8.
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- Date Issued: 2007
Photochemistry, photophysics and nonlinear optical parameters of phenoxy and tert-butylphenoxy substituted indium (III) phthalocyanines
- Authors: Chauke, Vongani , Durmus, Mahmut , Nyokong, Tebello
- Date: 2007
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268823 , vital:54235 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.05.022"
- Description: This work hereby presents the syntheses, photochemistry and photophysics of octaphenoxy ((Cl)InOPPc) and octakis(4-tert-butylphenoxy)chloroindium ((Cl)InOTBPPc) phthalocyanines. Calculated nonlinear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. Fluorescence quantum yields do not vary much between (Cl)InOPPc and (Cl)InOTBPPc complexes in different solvents. High quantum yields of triplet state (ΦT ranging from 0.70 to 0.91 in dimethysulphoxide, DMSO) and singlet oxygen generation (ΦΔ, ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50–60 μs were obtained in DMSO). The optical limiting threshold intensity (Ilim) for the InPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The latter were found to be better optical limiters.
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- Date Issued: 2007