Synthesis, spectroscopic and electrochemical properties of manganese, nickel and iron octakis-(2-diethylaminoethanethiol)-phthalocyanine
- Adebayo, A I, Nyokong, Tebello
- Authors: Adebayo, A I , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6563 , http://hdl.handle.net/10962/d1004122
- Description: The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.
- Full Text:
- Date Issued: 2009
- Authors: Adebayo, A I , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6563 , http://hdl.handle.net/10962/d1004122
- Description: The syntheses, spectroscopic and electrochemical properties of manganese (3), nickel (4) and iron (5) phthalocyanine complexes, octa-substituted at the peripheral positions with diethlyaminoethanethiol substituent, are reported. The electrochemistry of these complexes and the corresponding cobalt complex (6) are reported. Complex 3 showed two reversible reduction couples attributed to the MnIIIPc−2/MnIIPc−2 (E½ = −0.12 V versus Ag|AgCl) and MnIIPc−2/MnIIPc−3 (E½ = −0.82 V versus Ag|AgCl) species. Two ring-based reduction couples were also observed for complex 4. Two reduction couples, assigned to the FeIIPc−2/FeIPc−2 (E½ = −0.35 V versus Ag|AgCl) and FeIPc−2/FeIPc−3 (E½ = −0.96 V versus Ag|AgCl) species, and an oxidation couple, attributed to FeIIIPc−2/FeIIPc−2 (E½ = 0.26 V versus Ag|AgCl) species, were observed. For complex 6, two reductions and one oxidation were also observed with the potential range of 1.2 to −1.8 V versus Ag|AgCl Spectroelectrochemical studies were used to confirm some of the assigned processes.
- Full Text:
- Date Issued: 2009
Structural and optical properties of alloyed quaternary CdSeTeS core and CdSeTeS/ZnS core–shell quantum dots
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7244 , http://hdl.handle.net/10962/d1020248
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface. , Original publication is available at http://dx.doi.org/10.1016/j.jallcom.2015.05.083
- Full Text: false
- Date Issued: 2015
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7244 , http://hdl.handle.net/10962/d1020248
- Description: Synthesis of fluorescent alloyed quantum dots (QDs) with unique optical properties suitable for a wide array of chemical, physical and biological applications is of research interest. In this work, highly luminescent and photostable alloyed quaternary CdSeTeS core QDs of two different sizes were fabricated via the organometallic hot-injection synthetic route. Characterization of the nanocrystals were performed using TEM, XRD, UV/vis and fluorescence spectrophotometric techniques. We have demonstrated in this work that the well fabricated alloyed quaternary CdSeTeS core QDs possess unique optical properties that are advantageous over conventional core/shell systems. Formation of the CdSeTeS/ZnS core/shell with the desired optical properties comes with a number of challenges, hence the advantages of the quaternary alloyed core over the core/shell QDs are (i) avoidance of the challenging process of determining the proper shell thickness which can provide the desired optical properties in the core/shell system and (ii) avoidance of the lattice-induced mismatch between the core and the shell material which can either lead to incomplete exciton confinement or dislocation at the core/shell interface. , Original publication is available at http://dx.doi.org/10.1016/j.jallcom.2015.05.083
- Full Text: false
- Date Issued: 2015
Optical properties of water-soluble l-cysteine-capped alloyed CdSeS quantum dot passivated with ZnSeTe and ZnSeTe/ZnS shells
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7260 , http://hdl.handle.net/10962/d1020269
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.024
- Full Text: false
- Date Issued: 2015
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7260 , http://hdl.handle.net/10962/d1020269
- Description: Alloyed quantum dots (QDs) passivated with shell materials have valuable optical characteristics suitable for a wide array of applications. In this work, alloyed ternary CdSeS QDs passivated with ZnSeTe and ZnSeTe/ZnS shells have been synthesized via a hot-injection method and a ligand exchange reaction employing l-cysteine as a thiol ligand has been used to obtain these water-soluble nanocrystals for the first time. The photoluminescence (PL) quantum yield (QY) of alloyed l-cysteine-capped CdSeS was 71.2% but decreased significantly to 5.2% upon passivation with a ZnSeTe shell. The red shift in PL emission of the CdSeS/ZnSeTe QDs was attributed to be strain-induced whilst a lattice-induced process likely created defect states in the core/shell interface hence contributing to the decline in the PL QY. Nonetheless, the fluorescence stability of CdSeS/ZnSeTe QDs in aqueous solution was unperturbed. Further passivation with a ZnS shell (CdSeS/ZnSeTe/ZnS) improved the PL QY to a value of 58.7% and thus indicates that the defect state in the QDs core/shell/shell structure was reduced. PL lifetime exciton measurements indicated that the rates of decay of the QDs influenced their photophysical properties. , Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.024
- Full Text: false
- Date Issued: 2015
Deposition of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shells around CdSeTe alloyed core quantum dots: effects on optical properties
- Adegoke, Oluwasesan, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7289 , http://hdl.handle.net/10962/d1020342
- Description: In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs. Copyright © 2015 John Wiley & Sons, Ltd. , Original publication is available at http://dx.doi.org/10.1002/bio.3013
- Full Text: false
- Date Issued: 2015
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7289 , http://hdl.handle.net/10962/d1020342
- Description: In this work, we synthesized water-soluble L-cysteine-capped alloyed CdSeTe core quantum dots (QDs) and investigated the structural and optical properties of deposition of each of CdS, CdS/ZnSe and CdS/ZnSe/ZnS shell layers. Photophysical results showed that the overcoating of a CdS shell around the alloyed CdSeTe core [quantum yield (QY) = 8.4%] resulted in effective confinement of the radiative exciton with an improved QY value of 93.5%. Subsequent deposition of a ZnSe shell around the CdSeTe/CdS surface decreased the QY value to 24.7%, but an increase in the QY value of up to 49.5% was observed when a ZnS shell was overcoated around the CdSeTe/CdS/ZnSe surface. QDs with shell layers showed improved stability relative to the core. Data obtained from time-resolved fluorescence measurements provided useful insight into variations in the photophysical properties of the QDs upon the formation of each shell layer. Our study suggests that the formation of CdSeTe/CdS core/shell QDs meets the requirements of quality QDs in terms of high photoluminescence QY and stability, hence further deposition of additional shells are not necessary in improving the optical properties of the core/shell QDs. Copyright © 2015 John Wiley & Sons, Ltd. , Original publication is available at http://dx.doi.org/10.1002/bio.3013
- Full Text: false
- Date Issued: 2015
Unsymmetrically Substituted Nickel Triazatetra-Benzcorrole and Phthalocynanine Complexes: Conjugation to Quantum Dots and Applications as Fluorescent “Turn ON” Sensors
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7311 , http://hdl.handle.net/10962/d1020403
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs. , Original publication is available at http://dx.doi.org/10.1007/s10895-013-1317-4
- Full Text: false
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7311 , http://hdl.handle.net/10962/d1020403
- Description: We report on the design and application of fluorescent nanoprobes based on the covalent linking of L-glutathione-capped CdSe@ZnS quantum dots (QDs) to newly synthesized unsymmetrically substituted nickel mercaptosuccinic acid triazatetra-benzcorrole (3) and phthalocyanine (4) complexes. Fluorescence quenching of the QDs occurred on conjugation to complexes 3 or 4. The nanoprobes were selectively screened in the presence of different cations and Hg2+ showed excellent affinity in “turning ON” the fluorescence of the nanoprobes. Experimental results showed that the sensitivity of QDs-4 towards Hg2+ was much higher than that of QDs-3 nanoprobe. The mechanism of reaction has been elucidated based on the ability of Hg2+ to coordinate with the sulphur atom of the Ni complex ring and apparently “turn ON” the fluorescence of the linked QDs. , Original publication is available at http://dx.doi.org/10.1007/s10895-013-1317-4
- Full Text: false
Effects of analytes on the fluorescence properties of CdTe@ZnS quantum dots decorated with cobalt tetraamino-phthalocyanine
- Adegoke, Oluwasesan, Nyokong, Tebello
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7315 , http://hdl.handle.net/10962/d1020541
- Description: In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe. , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2013.09.079
- Full Text: false
- Authors: Adegoke, Oluwasesan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7315 , http://hdl.handle.net/10962/d1020541
- Description: In this work, we have carried out an investigation on the effects of different biologically active analytes on the fluorescence response of glutathione-capped CdTe@ZnS quantum dots (QDs)-colbalt tetraamino-phthalocyanine nanoconjugate system. Firstly, fluorescence quenching occurred. Experimental results showed that some analytes either “turned on”, others further quenched or showed no effect on the fluorescence emission of the nanoprobe. , Original publication is available at http://dx.doi.org/10.1016/j.jlumin.2013.09.079
- Full Text: false
Electrochemical properties of benzylmercapto and dodecylmercapto tetra substituted nickel phthalocyanine complexes: Electrocatalytic oxidation of nitrite
- Agboola, Bolade O, Ozoemena, Kenneth I, Nyokong, Tebello
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6562 , http://hdl.handle.net/10962/d1003826
- Description: Nickel tetrakis(benzylmercapto)phthalocyanine (NiTBMPc) and nickel tetrakis(dodecylmercapto)phthalocyanine (NiTDMPc) complexes were synthesized and their spectral and electrochemical properties reported. The CV showed four or five redox processes for NiTBMPc and NiTDMPc, respectively. For the first time, spectroelectrochemistry gave evidence for the formation of NiII/NiI process in a NiPc complex. The rest of the processes were ring based. The NiTBMPc complex was successfully deposited on both gold and glassy carbon electrodes by electropolymerisation while NiTDMPc complex was deposited on gold electrode only. The films were electro-transformed in aqueous 0.1 M NaOH solution to the O–Ni–O oxo bridged form. The modified electrodes were characterized using electrochemical impedance spectroscopy and the results showed typical behavior for modified electrodes. Electrodes with poly-Ni(OH)Pcs films exhibited higher charge transfer resistance values, Rp than their corresponding poly-NiPcs films counterparts. All the modified electrodes showed improved catalytic activities than the unmodified electrodes towards nitrite ions electrooxidation. Better catalytic activities were observed for the modified electrodes when they were transformed to O–Ni–O oxo bridge form. All the modified electrodes exhibited high resistance to electrode surface passivation.
- Full Text:
- Date Issued: 2006
- Authors: Agboola, Bolade O , Ozoemena, Kenneth I , Nyokong, Tebello
- Date: 2006
- Language: English
- Type: Article
- Identifier: vital:6562 , http://hdl.handle.net/10962/d1003826
- Description: Nickel tetrakis(benzylmercapto)phthalocyanine (NiTBMPc) and nickel tetrakis(dodecylmercapto)phthalocyanine (NiTDMPc) complexes were synthesized and their spectral and electrochemical properties reported. The CV showed four or five redox processes for NiTBMPc and NiTDMPc, respectively. For the first time, spectroelectrochemistry gave evidence for the formation of NiII/NiI process in a NiPc complex. The rest of the processes were ring based. The NiTBMPc complex was successfully deposited on both gold and glassy carbon electrodes by electropolymerisation while NiTDMPc complex was deposited on gold electrode only. The films were electro-transformed in aqueous 0.1 M NaOH solution to the O–Ni–O oxo bridged form. The modified electrodes were characterized using electrochemical impedance spectroscopy and the results showed typical behavior for modified electrodes. Electrodes with poly-Ni(OH)Pcs films exhibited higher charge transfer resistance values, Rp than their corresponding poly-NiPcs films counterparts. All the modified electrodes showed improved catalytic activities than the unmodified electrodes towards nitrite ions electrooxidation. Better catalytic activities were observed for the modified electrodes when they were transformed to O–Ni–O oxo bridge form. All the modified electrodes exhibited high resistance to electrode surface passivation.
- Full Text:
- Date Issued: 2006
Tuning the physico-electrochemical properties of novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine complex using phenylamine-functionalised SWCNTs
- Agboola, Bolade Oyeyinka, Ozoemena, Kenneth I., Nyokong, Tebello, Fukuda, Takamitsu, Kobayashi, Nagao
- Authors: Agboola, Bolade Oyeyinka , Ozoemena, Kenneth I. , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Language: English
- Type: Article
- Identifier: vital:7238 , http://hdl.handle.net/10962/d1019689
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode. , Original publication is available at http://dx.doi.org/doi:10.1016/j.carbon.2009.10.023
- Full Text: false
- Authors: Agboola, Bolade Oyeyinka , Ozoemena, Kenneth I. , Nyokong, Tebello , Fukuda, Takamitsu , Kobayashi, Nagao
- Language: English
- Type: Article
- Identifier: vital:7238 , http://hdl.handle.net/10962/d1019689
- Description: The integration of phenylamine-functionalised SWCNTs (SWCNT-phenylamine) with a novel cobalt (II) octa[(3,5-biscarboxylate)-phenoxy] phthalocyanine (CoOBPPc) complex has been described. The physical and electrochemical properties of the CoOBPPc-SWCNT-phenylamine hybrid were evaluated using spectroscopy (IR and UV–vis), field emission scanning electron microscopy and electrochemistry (cyclic voltammetry and electrochemical impedance spectroscopy). Integration of SWCNT-phenylamine resulted in the physical transformation of the CoOBCPPc from the usually bluish colour of cobalt phthalocyanine complexes to a beautiful bright green colour. In addition, the heterogeneous electron transfer kinetics and electrocatalytic properties of the CoOBCPPc were greatly enhanced following the attachment of the SWCNT-phenylamine. The potential electrocatalytic application of the hybrid was tested using β-nicotinamide adenine dinucleotide (NADH) as a model biological analyte. Interestingly, the onset oxidation potential of this analyte was significantly reduced (300 mV) by this hybrid compared to the bare electrode. , Original publication is available at http://dx.doi.org/doi:10.1016/j.carbon.2009.10.023
- Full Text: false
Photophysical and nonlinear optical studies of tetraakynyl zincphthalocyanine and its “clicked” analogue
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7251 , http://hdl.handle.net/10962/d1020259
- Description: We report here for the first time on the photophysical and nonlinear optical behavior of tetra-substituted alkynyl zinc phthalocyanine and its “clicked” analogue (4 and 5). The compounds exhibited high triplet quantum yields in dimethylsulphoxide (DMSO). Nonlinear optical (NLO) properties were also evaluated for the two compounds at 532 nm and 10 ns in DMSO. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The presence of electron acceptor groups fused with triazole linkers in the peripheral positions of 4 provide excellent coexistent features, such as enhanced triplet quantum yields and lifetimes compared to 5. Large third-order susceptibility (2.09 × 10−11 and 3.53 × 10−9 esu) and hyperpolarizability (1.09 × 10−30 and 9.13 × 10−29 esu) were estimated for complexs 4 and 5, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.01.048
- Full Text: false
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7251 , http://hdl.handle.net/10962/d1020259
- Description: We report here for the first time on the photophysical and nonlinear optical behavior of tetra-substituted alkynyl zinc phthalocyanine and its “clicked” analogue (4 and 5). The compounds exhibited high triplet quantum yields in dimethylsulphoxide (DMSO). Nonlinear optical (NLO) properties were also evaluated for the two compounds at 532 nm and 10 ns in DMSO. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The presence of electron acceptor groups fused with triazole linkers in the peripheral positions of 4 provide excellent coexistent features, such as enhanced triplet quantum yields and lifetimes compared to 5. Large third-order susceptibility (2.09 × 10−11 and 3.53 × 10−9 esu) and hyperpolarizability (1.09 × 10−30 and 9.13 × 10−29 esu) were estimated for complexs 4 and 5, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.01.048
- Full Text: false
Mercaptopyridine-substituted indium, zinc, and metal-free phthalocyanines: nonlinear optical studies in solution and on polymer matrices
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7278 , http://hdl.handle.net/10962/d1020313
- Description: In this article, the nonlinear optical characterizations and optical limiting properties of metal-free (2), zinc (3), and indium (4) tetra 4-(2-mercaptopyridine) phthalocyanines are discussed. Nonlinear optical properties of the samples were evaluated using Z-scan at 532 nm and 10 ns pulse in CHCl3, and doped on poly(bisphenol A carbonate) (PBC) thin films. Thin films for 2, 3, and 4 are represented as 2-PBC, 3-PBC, and 4-PBC, respectively. We observed two-photon absorption (2PA) and strong reverse saturable absorption as the dominant mechanisms at nanosecond laser excitation in solution and thin films. By virtue of the magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work, sample 4 was found to exhibit strongest nonlinear optical properties followed by 3, while 2 is the weakest nonlinear absorber of the studied samples. Large third-order susceptibility (1.46 × 10−9 esu and 7.74 × 10−10 esu) and hyperpolarizability (2.13 × 10−28 and 8.37 × 10−29 esu) were estimated for 4-PBC and 3-PBC, respectively. Our studies show that these molecules are suitable candidates for practical passive optical limiters. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1077237
- Full Text: false
- Date Issued: 2015
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2015
- Language: English
- Type: Article
- Identifier: vital:7278 , http://hdl.handle.net/10962/d1020313
- Description: In this article, the nonlinear optical characterizations and optical limiting properties of metal-free (2), zinc (3), and indium (4) tetra 4-(2-mercaptopyridine) phthalocyanines are discussed. Nonlinear optical properties of the samples were evaluated using Z-scan at 532 nm and 10 ns pulse in CHCl3, and doped on poly(bisphenol A carbonate) (PBC) thin films. Thin films for 2, 3, and 4 are represented as 2-PBC, 3-PBC, and 4-PBC, respectively. We observed two-photon absorption (2PA) and strong reverse saturable absorption as the dominant mechanisms at nanosecond laser excitation in solution and thin films. By virtue of the magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work, sample 4 was found to exhibit strongest nonlinear optical properties followed by 3, while 2 is the weakest nonlinear absorber of the studied samples. Large third-order susceptibility (1.46 × 10−9 esu and 7.74 × 10−10 esu) and hyperpolarizability (2.13 × 10−28 and 8.37 × 10−29 esu) were estimated for 4-PBC and 3-PBC, respectively. Our studies show that these molecules are suitable candidates for practical passive optical limiters. , Original publication is available at http://dx.doi.org/10.1080/00958972.2015.1077237
- Full Text: false
- Date Issued: 2015
Photophysical and non-linear optical behavior of novel tetra alkynyl terminated indium phthalocyanines: Effects of the carbon chain length
- Bankole, Owolabi M, Britton, Jonathan, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7262 , http://hdl.handle.net/10962/d1020271
- Description: We report on the synthesis, photophysical and nonlinear optical behavior of tetra-substituted alkynyl indium phthalocyanine complexes (3a and 3b). Both complexes showed large triplet quantum yields. Nonlinear optical properties were also evaluated for the two complexes at a wavelength of 532 nm using nanosecond Z-scan technique in dimethylsulfoxide. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The underlining 2PA and observed RSA were subjected to further scrutiny by comparing the analytical absorption model to the transmittance optical absorption theory. The theoretical results were in good agreement to the observed RSA and the 2PA mechanism. Large two-photon absorption cross-section (1.29 × 10−42 and 1.15 × 10−42 cm4 s/photon), third-order susceptibility (2.10 × 10−14 and 2.15 × 10−14 esu) and hyperpolarizability (2.70 × 10−32 and 3.19 × 10−32 esu) were estimated for complex 3a and 3b, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.12.020
- Full Text: false
- Authors: Bankole, Owolabi M , Britton, Jonathan , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7262 , http://hdl.handle.net/10962/d1020271
- Description: We report on the synthesis, photophysical and nonlinear optical behavior of tetra-substituted alkynyl indium phthalocyanine complexes (3a and 3b). Both complexes showed large triplet quantum yields. Nonlinear optical properties were also evaluated for the two complexes at a wavelength of 532 nm using nanosecond Z-scan technique in dimethylsulfoxide. We observed two-photon absorption (2PA) and strong reverse saturable absorption (RSA) as the dominant mechanisms at nanosecond laser excitation. The underlining 2PA and observed RSA were subjected to further scrutiny by comparing the analytical absorption model to the transmittance optical absorption theory. The theoretical results were in good agreement to the observed RSA and the 2PA mechanism. Large two-photon absorption cross-section (1.29 × 10−42 and 1.15 × 10−42 cm4 s/photon), third-order susceptibility (2.10 × 10−14 and 2.15 × 10−14 esu) and hyperpolarizability (2.70 × 10−32 and 3.19 × 10−32 esu) were estimated for complex 3a and 3b, respectively. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.12.020
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Surface electrochemistry : structured electrode, synthesis, and characterization
- Bedioui, Fethi, Nyokong, Tebello, Zagal, Jose H
- Authors: Bedioui, Fethi , Nyokong, Tebello , Zagal, Jose H
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6567 , http://hdl.handle.net/10962/d1004126 , http://dx.doi.org/10.1155/2012/405825
- Description: From introduction: The aim of this special issue is to show, through recent updated significant examples, how the electrochemical techniques allow the unique characterization of specific properties of micro- and nanostructured materials that offer varied possibilities of uses and the preparation of specific types of ordered materials that take advantage of electrochemical synthetic methods such as structuring nanosized wires and dots, to cite only two examples.
- Full Text:
- Date Issued: 2012
- Authors: Bedioui, Fethi , Nyokong, Tebello , Zagal, Jose H
- Date: 2012
- Language: English
- Type: Article
- Identifier: vital:6567 , http://hdl.handle.net/10962/d1004126 , http://dx.doi.org/10.1155/2012/405825
- Description: From introduction: The aim of this special issue is to show, through recent updated significant examples, how the electrochemical techniques allow the unique characterization of specific properties of micro- and nanostructured materials that offer varied possibilities of uses and the preparation of specific types of ordered materials that take advantage of electrochemical synthetic methods such as structuring nanosized wires and dots, to cite only two examples.
- Full Text:
- Date Issued: 2012
Fluorescence studies of quantum dots and zinc tetraamino phthalocyanine conjugates
- Britton, Jonathan, Antunes, Edith M, Nyokong, Tebello
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6565 , http://hdl.handle.net/10962/d1004124
- Description: CdTe Qds capped with mercapto propionic acid (MPA) were covalently linked to zinc tetraamino phthalocyanine (ZnTAPc) 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 the formation of an amide bond between ZnTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and a mixture of QDs and ZnTAPc (i.e. without chemical linking) showed Förster resonance energy transfer (FRET). ZnTAPc quenched the QDs emission, giving quenching constants in the order of 103 M−1.
- Full Text:
- Date Issued: 2009
- Authors: Britton, Jonathan , Antunes, Edith M , Nyokong, Tebello
- Date: 2009
- Language: English
- Type: Article
- Identifier: vital:6565 , http://hdl.handle.net/10962/d1004124
- Description: CdTe Qds capped with mercapto propionic acid (MPA) were covalently linked to zinc tetraamino phthalocyanine (ZnTAPc) 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 the formation of an amide bond between ZnTAPc and CdTe QDs. Both the linked ZnTAPc–QD complexes and a mixture of QDs and ZnTAPc (i.e. without chemical linking) showed Förster resonance energy transfer (FRET). ZnTAPc quenched the QDs emission, giving quenching constants in the order of 103 M−1.
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- Date Issued: 2009
Corrole–BODIPY conjugates: enhancing the fluorescence and phosphorescence of the corrole complex via efficient through bond energy transfer
- Chen, Wei, Zhang, Jianfeng, Mack, John, Kubheka, Gugu Patience, Nyokong, Tebello, Shen, Zhen, Wei Chen
- Authors: Chen, Wei , Zhang, Jianfeng , Mack, John , Kubheka, Gugu Patience , Nyokong, Tebello , Shen, Zhen , Wei Chen
- Date: 2015-06-08
- Subjects: RSC Advances (2015), 5, 50962-50967, doi:10.1039/C5RA07250F
- Language: English
- Type: Article
- Identifier: vital:7268 , http://hdl.handle.net/10962/d1020277
- Description: New corrole–BODIPY conjugates have been synthesized in high yield under mild conditions. Upon excitation at the absorption maximum of the BODIPY antenna chromophore, the fluorescence intensity of the free base corrole–BODIPY conjugate increases by ca. 300%, and significant phosphorescence intensity is observed for the iridium(III) complex of the conjugate, while almost no phosphorescence is observed for the parent iridium(III) corrole, due to through-bond energy transfer from the BODIPY antenna-chromophore to the corrole core. , Original publication is available at http://dx.doi.org/10.1039/c5ra07250f , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
- Full Text:
- Authors: Chen, Wei , Zhang, Jianfeng , Mack, John , Kubheka, Gugu Patience , Nyokong, Tebello , Shen, Zhen , Wei Chen
- Date: 2015-06-08
- Subjects: RSC Advances (2015), 5, 50962-50967, doi:10.1039/C5RA07250F
- Language: English
- Type: Article
- Identifier: vital:7268 , http://hdl.handle.net/10962/d1020277
- Description: New corrole–BODIPY conjugates have been synthesized in high yield under mild conditions. Upon excitation at the absorption maximum of the BODIPY antenna chromophore, the fluorescence intensity of the free base corrole–BODIPY conjugate increases by ca. 300%, and significant phosphorescence intensity is observed for the iridium(III) complex of the conjugate, while almost no phosphorescence is observed for the parent iridium(III) corrole, due to through-bond energy transfer from the BODIPY antenna-chromophore to the corrole core. , Original publication is available at http://dx.doi.org/10.1039/c5ra07250f , Arbortext Advanced Print Publisher 9.1.510/W Unicode , Acrobat Distiller 8.1.0 (Windows); modified using iText� 5.3.3 �2000-2012 1T3XT BVBA (AGPL-version)
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Characterization of amine-functionalized single-walled carbon nanotube-low symmetry phthalocyanine conjugates
- Chidawanyika, Wadzanai J U, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7237 , http://hdl.handle.net/10962/d1019688
- Description: Functionalization of single-walled carbon nanotubes (SWCNTs) with amine groups using a previously developed diazonium approach, followed by reaction with a carboxylic acid moiety allows direct attachment by an amide bond. We have developed a new SWCNT-low symmetry phthalocyanine conjugate using this approach, using dicyclohexylcarbodiimide as an activating agent to facilitate formation of an amide bond to give a covalently linked conjugate. A conjugate formed by non-covalent attachment has been used for a comparative investigation by FT-IR, Raman, and UV–Vis spectroscopies, and thermal gravimetric analysis. The fluorescence of the phthalocyanine is quenched in the conjugate. , Original publication is available at http://dx.doi.org/10.1016/j.carbon.2010.04.015
- Full Text: false
- Authors: Chidawanyika, Wadzanai J U , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7237 , http://hdl.handle.net/10962/d1019688
- Description: Functionalization of single-walled carbon nanotubes (SWCNTs) with amine groups using a previously developed diazonium approach, followed by reaction with a carboxylic acid moiety allows direct attachment by an amide bond. We have developed a new SWCNT-low symmetry phthalocyanine conjugate using this approach, using dicyclohexylcarbodiimide as an activating agent to facilitate formation of an amide bond to give a covalently linked conjugate. A conjugate formed by non-covalent attachment has been used for a comparative investigation by FT-IR, Raman, and UV–Vis spectroscopies, and thermal gravimetric analysis. The fluorescence of the phthalocyanine is quenched in the conjugate. , Original publication is available at http://dx.doi.org/10.1016/j.carbon.2010.04.015
- Full Text: false
The effects of gold coated and uncoated zinc oxide nanohexagons on the photophysicochemical properties of the low symmetry zinc phthalocyanine
- D'Souza, Sarah, Ogbodu, Racheal O, Nyokong, Tebello
- Authors: D'Souza, Sarah , Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7280 , http://hdl.handle.net/10962/d1020317
- Description: A new low symmetry, Zn phthalocyanine monosubstituted with diethylaminoethanethiol (mDEAET ZnPc) was synthesized and characterized. This work reports on its photophysical and photochemical properties of mDEAET ZnPc alone and when conjugated to gold coated and uncoated zinc oxide nanohexagons (ZnO NHXs). The photophysicochemical properties generally improved in the presence of the ZnO NHXs. These complexes were also tested for their photodynamic antimicrobial activity against Staphylococcus aureus (S. aureus). The Pc alone showed remarkable growth inhibition even at concentrations as low as 0.05 mg/mL. The conjugates showed a high photoinactivation of S. aureus after 30 min at a fluence of 90 mW cm−2 at a concentration of 0.05 mg/mL. The ZnPc-ZnO NHX conjugates produced the best antimicrobial results. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.06.088
- Full Text: false
- Authors: D'Souza, Sarah , Ogbodu, Racheal O , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7280 , http://hdl.handle.net/10962/d1020317
- Description: A new low symmetry, Zn phthalocyanine monosubstituted with diethylaminoethanethiol (mDEAET ZnPc) was synthesized and characterized. This work reports on its photophysical and photochemical properties of mDEAET ZnPc alone and when conjugated to gold coated and uncoated zinc oxide nanohexagons (ZnO NHXs). The photophysicochemical properties generally improved in the presence of the ZnO NHXs. These complexes were also tested for their photodynamic antimicrobial activity against Staphylococcus aureus (S. aureus). The Pc alone showed remarkable growth inhibition even at concentrations as low as 0.05 mg/mL. The conjugates showed a high photoinactivation of S. aureus after 30 min at a fluence of 90 mW cm−2 at a concentration of 0.05 mg/mL. The ZnPc-ZnO NHX conjugates produced the best antimicrobial results. , Original publication is available at http://dx.doi.org/10.1016/j.molstruc.2015.06.088
- Full Text: false
Synthetic pathways to water-soluble phthalocyanines and close analogs
- Dumoulin, Fabienne, Durmus, Mahmut, Ahsen, Vefa, Nyokong, Tebello
- Authors: Dumoulin, Fabienne , Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7240 , http://hdl.handle.net/10962/d1019720
- Description: The different types of water-soluble phthalocyanines are presented and their synthesis is reviewed. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.002
- Full Text: false
- Authors: Dumoulin, Fabienne , Durmus, Mahmut , Ahsen, Vefa , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7240 , http://hdl.handle.net/10962/d1019720
- Description: The different types of water-soluble phthalocyanines are presented and their synthesis is reviewed. , Original publication is available at http://dx.doi.org/10.1016/j.ccr.2010.05.002
- Full Text: false
Photophysicochemical and Fluorescence quenching studies of benzyloxyphenoxy substituted zinc phthalocyanines
- Durmuş, Mahmut, Nyokong, Tebello
- Authors: Durmuş, Mahmut , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
- Authors: Durmuş, Mahmut , Nyokong, Tebello
- Date: 2008
- Language: English
- Type: Article
- Identifier: vital:6570 , http://hdl.handle.net/10962/d1004133
- Description: Photochemical and photophysical measurements were conducted on peripheral and non-peripheral tetrakis- and octakis(4-benzyloxyphenoxy)-substituted zinc phthalocyanines (1, 2 and 3). General trends are described for photodegradation, and fluorescence quantum yields, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds in dimethylsulphoxide (DMSO) and toluene. The fluorescence of the complexes is quenched by benzoquinone (BQ), and fluorescence quenching properties are investigated in DMSO and toluene. The effects of the solvents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (1, 2 and 3) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications.
- Full Text:
- Date Issued: 2008
Effects of ZnO nanohexagons and nanorods on the fluorescence behavior of metallophthalocyanines
- D’Souza, Sarah, Moeno, Sharon, Nyokong, Tebello
- Authors: D’Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7263 , http://hdl.handle.net/10962/d1020272
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.09.012
- Full Text: false
- Authors: D’Souza, Sarah , Moeno, Sharon , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7263 , http://hdl.handle.net/10962/d1020272
- Description: This paper looks at the fluorescence behavior of zinc phthalocyanines: 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptoacetic acid phthalocyaninato) zinc(II) (ZnTMAAPc), 2,(3),9(10),16(17),23(24)-tetrakis-(mercaptopropanoic acid phthalocyaninato) zinc(II) (ZnTMPAPc) and (OH)AlPcSmix (the latter contains a mixture of the di-, tri- and tetra-sulfonated derivatives with an average of three sulfonated groups per molecule) in the presence of ZnO nanoparticles. Fluorescence lifetimes of Pc complexes generally decreased in the presence of ZnO nanoparticles, with generally longer lifetimes for ZnO nanohexagons compared to ZnO nanorods. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.09.012
- Full Text: false
Enhanced triplet state yields in aqueous media of asymmetric zinc phthalocyanines when conjugated to silver nanoflowers
- D’Souza, Sarah, George, Reama, Göksel, Meltem, Atilla, Devrim, Durmuş, Mahmut, Nyokong, Tebello
- Authors: D’Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmuş, Mahmut , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7279 , http://hdl.handle.net/10962/d1020315
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.08.017
- Full Text: false
- Authors: D’Souza, Sarah , George, Reama , Göksel, Meltem , Atilla, Devrim , Durmuş, Mahmut , Nyokong, Tebello
- Language: English
- Type: Article
- Identifier: vital:7279 , http://hdl.handle.net/10962/d1020315
- Description: Novel low symmetry water-soluble zinc phthalocyanines (ZnPcs, complexes 1 and 2) were synthesized and then mixed with silver nanoflowers. Photophysical and photochemical studies were performed in order to determine the efficiency of complexes 1 and 2 as photosensitizers when alone and when combined with the silver nanoflowers. The Pcs show low fluorescence quantum yields and excellent triplet quantum yields of 0.78 (for 1) and 0.66 (for 2) in aqueous media. The triplet quantum yield values increased to 0.80 and 0.89, respectively, in the presence of silver nanoflowers. Long triplet lifetimes ranging from 180 to 200 μs in DMSO were obtained for complexes 1, 2 and their conjugates with silver nanoflowers. , Original publication is available at http://dx.doi.org/10.1016/j.poly.2015.08.017
- Full Text: false