Photophysical and photoelectrochemical properties of water soluble metallophthalocyanines
- Authors: Masilela, Nkosiphile
- Date: 2010
- Subjects: Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4330 , http://hdl.handle.net/10962/d1004991 , Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Description: This work presents the synthesis, characterization, photophysicochemical and photoelectrochemical properties of anionic octa-caboxylated (MOCPcs), tetra-sulfonated (MTSPcs) and quaternized cationic (Q(T-2-Py)MPcs) water soluble aluminium, gallium, silicon, titanium and zinc phthalocynines. The peripherally tetra-substituted cationic (Q(T-2-Py)MPcs) and anionic (MTSPcs) were found to be aggregated in aqueous media, yet the octa-carboxylated (MOCPcs) counterparts were monomeric in solution. Cremophor EL (CEL) was used as a disaggregating agent, all the aggregated complexes disaggregated partially or completely in the presence of CEL. The photophysicochemical properties of aggregated complexes were investigated both in the presence of CEL and in aqueous media of pH 11 alone. Low triplet, singlet oxygen and fluorescence quantum yield were obtained in aqueous media (especially for the aggregated complexes) but a high improvement was achieved upon addition of CEL. The gallium complexes ((OH)GaOCPc and (OH)GaTSPc) showed good photophysicochemical properties with higher triplet and singlet oxygen quantum yields. For photoelectrochemistry the (MPcs) dyes were adsorbed to nanoporous ZnO, electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. Quaternized cationic (Q(T-2-Py)MPc) and tetrasulfonated (MTSPcs) phthalocyanines formed strong aggregates when deposited on the surface of FTO/ZnO substrate leading. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for quaternized and tetrasulfonated metallophthalocyanines because of the strong aggregates when they were on the surface of the electrodes. Among the studied materials, OTiOCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of so far = 0.48%.
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- Authors: Masilela, Nkosiphile
- Date: 2010
- Subjects: Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4330 , http://hdl.handle.net/10962/d1004991 , Phthalocyanines , Electrochemistry , Photoelectrochemistry
- Description: This work presents the synthesis, characterization, photophysicochemical and photoelectrochemical properties of anionic octa-caboxylated (MOCPcs), tetra-sulfonated (MTSPcs) and quaternized cationic (Q(T-2-Py)MPcs) water soluble aluminium, gallium, silicon, titanium and zinc phthalocynines. The peripherally tetra-substituted cationic (Q(T-2-Py)MPcs) and anionic (MTSPcs) were found to be aggregated in aqueous media, yet the octa-carboxylated (MOCPcs) counterparts were monomeric in solution. Cremophor EL (CEL) was used as a disaggregating agent, all the aggregated complexes disaggregated partially or completely in the presence of CEL. The photophysicochemical properties of aggregated complexes were investigated both in the presence of CEL and in aqueous media of pH 11 alone. Low triplet, singlet oxygen and fluorescence quantum yield were obtained in aqueous media (especially for the aggregated complexes) but a high improvement was achieved upon addition of CEL. The gallium complexes ((OH)GaOCPc and (OH)GaTSPc) showed good photophysicochemical properties with higher triplet and singlet oxygen quantum yields. For photoelectrochemistry the (MPcs) dyes were adsorbed to nanoporous ZnO, electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. Quaternized cationic (Q(T-2-Py)MPc) and tetrasulfonated (MTSPcs) phthalocyanines formed strong aggregates when deposited on the surface of FTO/ZnO substrate leading. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for quaternized and tetrasulfonated metallophthalocyanines because of the strong aggregates when they were on the surface of the electrodes. Among the studied materials, OTiOCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of so far = 0.48%.
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Symmetrically and unsymmetrically substituted carboxy phthalocyanines as sensitizers for nanoporous ZnO films
- Masilela, Nkosiphile, Nombona, Nolwazi, Loewenstein, Thomas, Nyokong, Tebello, Schlettwein, Derck
- Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
- Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
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- Authors: Masilela, Nkosiphile , Nombona, Nolwazi , Loewenstein, Thomas , Nyokong, Tebello , Schlettwein, Derck
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249126 , vital:51780 , xlink:href="https://doi.org/10.1142/S1088424610002793"
- Description: The photoelectroectrochemical studies of water soluble octacarboxylated oxotitanium (OTiOCPc), zinc (ZnOCPC), hydroxyaluminium ((OH)AlOCPc), dihydroxysilicon ((OH)2SiOCPc), hydroxygallium (OHGaOCPc) and low symmetry zinc monocarboxy (ZnMCPc) phthalocyanines were performed. The dyes were adsorbed to nanoporous ZnO electrodeposited in the presence of eosin Y as structure directing agent (SDA) on FTO substrates by refluxing or soaking the films in a solution containing the dye of interest such that a full surface coverage was achieved. High external (IPCE) and internal (APCE) quantum efficiencies of up to 50.6% and 96.7% were achieved for the OTiOCPc complex. There was a lower overall cell efficiency for cells sensitized with phthalocyanines containing hydroxyl as axial ligand ZnO/(OH)2SiOCPc, ZnO/(OH)GaOCPc and (OH)AlOCPc because of strong aggregation on the surface of the electrodes. To further suppress dye aggregation, the zinc complex of a new monocarboxylated phthalocyanine sensitizer with bulky naphtho side groups (ZnMCPc) was employed. Among the studied sensitizers, ZnMCPc gave the highest overall cell efficiency of phthalocyanine electrodeposited on ZnO of η = 0.48%.
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The synthesis and photophysical properties of novel cationic tetra pyridiloxy substituted aluminium, silicon and titanium phthalocyanines in water
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249159 , vital:51783 , xlink:href="https://doi.org/10.1016/j.jlumin.2010.04.011"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.
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- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/249159 , vital:51783 , xlink:href="https://doi.org/10.1016/j.jlumin.2010.04.011"
- Description: This work reports on the synthesis, characterisation and photophysical properties of new unquaternized β-2,(3)-tetra-(2 pyridiloxy) aluminium(III) (3a), silicon(IV) (3b), titanium(IV) (3c) phthalocyanines and their water-soluble quaternized counterparts, 4a, 4b and 4c, respectively. The water-soluble silicon(IV) (4b) and titanium(IV) (4c) phthalocyanine derivatives were found to be aggregated in aqueous media but were partially or fully disaggregated in the presence of a surfactant Cremophor® EL (CEL). The photophysical properties of aggregated complexes were investigated both in the presence of CEL and in pH 11 alone. Low triplet and fluorescence yield were obtained in pH 11 but an improvement was achieved upon addition of CEL for the aggregated complexes. The unquaternized silicon(IV) phthalocyanine complex (3b) gave the highest triplet quantum yield of 0.77 in DMF followed by its quaternized derivative (4b) with triplet yield of 0.73 in pH 11 plus CEL. The highest triplet lifetime of 220 μs was obtained for 4b in the presence of CEL. Higher fluorescence yields of 0.23 were obtained for quaternized water-soluble aluminium(III) phthalocyanine derivative (4a) in the presence of CEL.
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The synthesis and photophysical properties of water soluble tetrasulfonated, octacarboxylated and quaternised 2,(3)-tetra-(2 pyridiloxy) Ga phthalocyanines
- Masilela, Nkosiphile, Nyokong, Tebello
- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Language: English
- Type: Article
- Identifier: vital:6579 , http://hdl.handle.net/10962/d1004142
- Description: The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.
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- Authors: Masilela, Nkosiphile , Nyokong, Tebello
- Date: 2010
- Language: English
- Type: Article
- Identifier: vital:6579 , http://hdl.handle.net/10962/d1004142
- Description: The photophysical behaviour of chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine (ClGaT-2-PyPc) and its quaternised derivative were compared with that of the water soluble anionic tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydoxy gallium octacarboxy phthalocyanine ((OH)GaOCPc). Although both the quaternised compound and the tetrasulfonated gallium phthalocyanine aggregated in aq. solution at pH 11, resulting in low fluorescence and triplet yields, the presence of the surfactant Cremophore EL improved yields. Triplet quantum yields ranged from 0.52 to 0.70 and fluorescence quantum yields ranged from <0.01 to 0.21. The nature of substituent (sulfonate, carboxy and pyridiloxy) did not influence photophysical properties. Chlorogallium 2,(3)-tetra-(2 pyridiloxy) phthalocyanine and its quaternised derivative displayed longer triplet lifetime than both the tetrasulfonated gallium phthalocyanine ((OH)GaTSPc) and hydroxy gallium octacarboxy phthalocyanine in DMSO and in aq. media in both the presence and absence of surfactant.
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