The determination of the photosensitizing properties of mercapto substituted phthalocyanine derivatives in the presence of quantum dots capped with mercaptopropionic acid
- Authors: Moeno, Sharon , Antunes, Edith M , Nyokong, Tebello
- Date: 2011
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/247870 , vital:51625 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.12.009"
- Description: This work reports on the synthesis of several novel water soluble metallophthalocyanines containing Zn2+, In3+, Ga3+ or Si4+ as central metal ions and tetra substituted with mercaptoacetic acid and mercaptopropionic acid. The complexes were characterized using infra red, nuclear magnetic resonance and mass spectroscopies as well as elemental analysis. All the complexes are water soluble but the majority are highly aggregated in water and organic solvents. The complex containing Zn as a central metal and mercaptopropionic acid as a substituent was not aggregated allowing for the determination of photophysical parameters. This complex had triplet state quantum yield of 0.61 in DMF and 0.88 in DMSO while the fluorescence quantum yield was 0.13 in DMSO. The determination of photophysical properties of the complex containing Zn as a central metal and mercaptopropionic acid were carried out in the presence of mercaptopropionic acid capped CdTe quantum dots. There is an increase in triplet state quantum yield from 0.88 (for the phthalocyanine alone) to 0.94 (in the presence of CdTe quantum dots) in DMSO.
- Full Text:
- Date Issued: 2011
Fluorescence quenching and energy transfer in conjugates of quantum dots with zinc and indium tetraamino phthalocyanines
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/262638 , vital:53539 , xlink:href="https://doi.org/10.1016/j.jphotochem.2009.12.013"
- Description: CdTe QDs capped with mercapto propionic acid (MPA) and thioglycolic acid (TGA) were covalently linked to zinc and indium tetraaminophthalocyanines (TAPcs) using N-ethyl-N(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) as the coupling agents. The results presented give evidence in favour of formation of an amide bond between the MTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and the mixture of QDs and ZnTAPc (without chemical linking) showed Förster resonance energy transfer (FRET), whereas the QD interactions with InTAPc yielded no evidence of FRET. Both MTAPcs quenched the QDs emission, with quenching constants of the order of 103–104 M−1. High energy transfer efficiencies were obtained in some cases (as high as 93%), due to the low donor to acceptor distances.
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- Date Issued: 2010
Photophysical study of a covalently linked quantum dot–low symmetry phthalocyanine conjugate
- Authors: Chidawanyika, Wadzanai J U , Litwinski, Christian , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261641 , vital:53430 , xlink:href="https://doi.org/10.1016/j.jphotochem.2010.03.008"
- Description: The linkage of a low symmetry phthalocyanine, ZnttbIPc to mercaptopropionic acid (MPA) capped CdTe quantum dots has been achieved using a coupling agent, dicyclohexylcarbodiimide (DCC), to facilitate formation of an amide bond. UV–vis, Raman and IR spectroscopic studies on the linked (QD:ZnttbIPc-linked) conjugate suggest the reaction was a success. Förster resonance energy transfer (FRET) resulted in stimulated emission of ZnttbIPc in both the linked (QD:ZnttbIPc-linked) and mixed (QD:ZnttbIPc-mixed) conjugates. The linked complex (QD:ZnttbIPc-linked) gave the largest FRET efficiency hence showing the advantages of covalent linking. Photophysicochemical properties of the phthalocyanine were improved in the presence of the QDs i.e. for QD:ZnttbIPc-mixed. Fluorescence lifetimes of QDs were unchanged in QD:ZnttbIPc-mixed and decreased for QD:ZnttbIPc-linked.
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- Date Issued: 2010
The synthesis and fluorescence behaviour of phthalocyanines unsymmetrically substituted with naphthol and carboxy groups
- Authors: Nombona, Nolwazi , Antunes, Edith M , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/261534 , vital:53418 , xlink:href="https://doi.org/10.1016/j.dyepig.2009.11.010"
- Description: Unsymmetrically substituted phthalocyanines 8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanine, [8,15,22-tris-(naphtho)-2-(carboxy)phthalocyanato]zinc(II), 8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyanine and [8,15,22-tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenoxy)phthalocyanato]zinc(II) were prepared using the mixed phthalonitrile cyclotetramerization of 3-(1-naphthoxy) phthalonitrile with a carboxylic acid phthalonitrile. The phthalocyanines were separated using column chromatography employing a mixture of THF, ammonia and water. The novel compounds were characterized using UV–Vis, IR, 1H NMR and mass spectrometry as well as elemental analysis. Fluorescence quantum yields were found to range from 0.05 to 0.16.
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- Date Issued: 2010
Synthesis and solvent effects on the photophysicochemical properties of novel cadmium phenoxy phthalocyanines
- Authors: Chidawanyika, Wadzanai J U , Antunes, Edith M , Nyokong, Tebello
- Date: 2008
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/268649 , vital:54217 , xlink:href="https://doi.org/10.1016/j.jphotochem.2007.09.020"
- Description: The syntheses of novel cadmium phenoxy complexes; tetrakis{1,(4)-tert-butylphenoxyphthalocyaninato}cadmium(II) (5a), tetrakis{1,(4)-phenoxyphthalocyaninato}cadmium(II) (5b), tetrakis{2,(3)-tert-butylphenoxyphthalocyaninato}cadmium(II) (6a) and tetrakis{2,(3)-phenoxyphthalocyaninato}cadmium(II) (6b) are presented herein. The spectroscopic and photophysicochemical properties have also been carried out and discussed together with the influence of various organic solvents on these properties. Spectroscopic properties, i.e. ground state electronic absorption and fluorescence spectra have been found to vary as a function of substituent position on the phthalocyanine macrocycle, i.e. α-substitution versus β-substitution. The photophysical parameters are reported as well as the photodegradation and singlet oxygen quantum yields, where the complexes were found to exhibit good photostability with the production of appreciable amounts of singlet oxygen.
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- Date Issued: 2008
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
Photocatalysis of 4-nitrophenol using zinc phthalocyanine complexes
- Authors: Marais, Eloïse , 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
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.
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- Date Issued: 2007