A2B type copper (III) corroles containing zero-to-five fluorine atoms
- Li, Minzhi, Niu, Yingjie, Zhu, Weihua, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Liang, Xu
- Authors: Li, Minzhi , Niu, Yingjie , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238275 , vital:50604 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.10.044"
- Description: Four low symmetric A2B meso-substituted Cu(III)corroles with electron withdrawing meso-aryl rings have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to a series of DFT and TD-DFT calculations. A series of experiments demonstrate that these Cu(III)corroles can be used as highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, when the number of fluorine atoms at B meso-position is increased, there is a marked enhancement in the catalytic ability of the corrole complexes, which demonstrates that modification to the structures of low symmetry corroles is a useful strategy for developing new HER catalysts.
- Full Text:
- Date Issued: 2017
- Authors: Li, Minzhi , Niu, Yingjie , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/238275 , vital:50604 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.10.044"
- Description: Four low symmetric A2B meso-substituted Cu(III)corroles with electron withdrawing meso-aryl rings have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to a series of DFT and TD-DFT calculations. A series of experiments demonstrate that these Cu(III)corroles can be used as highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, when the number of fluorine atoms at B meso-position is increased, there is a marked enhancement in the catalytic ability of the corrole complexes, which demonstrates that modification to the structures of low symmetry corroles is a useful strategy for developing new HER catalysts.
- Full Text:
- Date Issued: 2017
Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine
- Martynov, Alexander G, Mack, John, Ngoy, Bokolombe P, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
- Authors: Martynov, Alexander G , Mack, John , Ngoy, Bokolombe P , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239643 , vital:50751 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.072"
- Description: A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution.
- Full Text:
- Date Issued: 2017
Enantioselective electrochemical carbon-chloride bond cleavage of hexachlorocyclohexanes (HCHs) catalyzed by Mn (III) Cl-phthalocyanine
- Wen, Junxia, Yu, Baoqui, Huang, Tingting, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Li, Minzhi, Zhu, Weihua, Liang, Xu
- Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
- Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
- Full Text:
- Date Issued: 2017
- Authors: Wen, Junxia , Yu, Baoqui , Huang, Tingting , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189252 , vital:44831 , xlink:href="https://doi.org/10.1016/j.jelechem.2017.09.020"
- Description: A lipophilic and electron-rich metallophthalocyanine Mn(III)Cl(α,α′-n-OC5H11)8Pc has been synthesized and characterized. A series of electrochemical experiments demonstrate that the Mn(III)Cl(α,α′-n-OC5H11)8Pc complex can be used as a catalyst for highly efficient carbon-chloride bond cleavage of environmental toxic hexachlorocyclohexanes (HCHs) through electrochemical catalysis, and that the increased catalytic efficiency is related to the enantiomeric carbon-chloride σ-bond of HCHs.
- Full Text:
- Date Issued: 2017
Halogen substituted A2B type Co (III) triarylcorroles
- Niu, Yingjie, Li, Minzhi, Zhang, Qianchong, Zhu, Weihua, Mack, John, Fomo, Gertrude, Nyokong, Tebello, Liang, Xu
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Date Issued: 2017
- Authors: Niu, Yingjie , Li, Minzhi , Zhang, Qianchong , Zhu, Weihua , Mack, John , Fomo, Gertrude , Nyokong, Tebello , Liang, Xu
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233048 , vital:50051 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.02.049"
- Description: Seven low symmetry A2B type Co(III)triarylcorroles with electron withdrawing meso-aryl substituents have been synthesized and characterized. A detailed analysis of the optical and redox properties has been carried out by comparing their optical spectroscopy, electrochemistry and spectroelectrochemistry to trends predicted in a series of DFT and TD-DFT calculations. The results demonstrate that Co(III)corroles are highly effective catalysts for hydrogen evolution reactions (HERs). Moreover, there is a marked enhancement in their homogenous catalytic ability when halogen atoms are introduced at the B position, which demonstrates that facile modifying the meso-aryl rings is a effective strategy for developing new HER catalysts. The electrochemical results demonstrate that an unusual two step modulation of HER reactions can be achieved by using singly and doubly electrochemical reduced cobalt triarylcorroles anions.
- Full Text:
- Date Issued: 2017
Highly efficient CCl bond cleavage and unprecedented CC bond cleavage of environmentally toxic DDT through molecular electrochemical catalysis
- Liang, Xu, Huang, Tingting, Li, Minzhi, Mack, John, Wildervanck, Martijn, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
- Authors: Liang, Xu , Huang, Tingting , Li, Minzhi , Mack, John , Wildervanck, Martijn , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188921 , vital:44798 , xlink:href="https://doi.org/10.1016/j.apcata.2017.07.026"
- Description: The electrocatalytic properties of a Co(II)octaalkoxyphthalocyanine complex (Co(II)Pc) with eight strongly electron-donating substituents provide the first example of the complete dechlorination of DDT through molecular electrocatalysis, rather than the use of metal electrodes which had been achieved previously. Interaction with a highly nucleophilic [Co(I)Pc]2− species results in rapid cleavage of the C(sp3) Cl, C(sp2) Cl and aromatic C(sp2) Cl bonds. Bis(p-chlorophenyl)methanone (BPCl2) is detected in high yield along with its full dechlorination product, diphenylmethanone (BP) and the conventional C Cl bond cleavage products, due to an unprecedented C C bond cleavage reaction that is followed by the formation of a C−O bond. Theoretical calculations are used to analyze trends in the electronic structure of the Co(II)octaalkoxyphthalocyanine complex that account for the efficiency of the C Cl bond cleavage reactions, and the reaction process and mechanism are analyzed in depth.
- Full Text:
- Date Issued: 2017
Improved nonlinear optical behaviour of ball type indium (III) phthalocyanine linked to glutathione capped nanoparticles
- Nwaji, Njemuwa, Oluwole, David O, Mack, John, Louzada, Marcel, Khene, Samson M, Britton, Jonathan, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Oluwole, David O , Mack, John , Louzada, Marcel , Khene, Samson M , Britton, Jonathan , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239654 , vital:50752 , xlink:href="https://doi.org/10.1016/j.dyepig.2017.01.066"
- Description: The synthesis of ball–type indium phthalocyanine (complex 4) and its covalent attachment to glutathione (GSH–) capped (Ag, Au, CdTeSe, CdTeSe/ZnO) nanoparticles are reported in this work. Furthermore, their photophysical and nonlinear optical behaviour were investigated. We observed a decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield of the nanoconjugates in comparison to complex 4 alone. The reverse saturable absorption was found to be dependent on excited state absorption. The optical limiting threshold ranges from 0.40–0.78 (J/cm2). The nanoconjugate of the complex 4 with GSH–CdTeSe/ZnO (QD1) accounted for the most improved triplet state parameters and nonlinear optical behaviour in comparison to complex 4 and the other nanoconjugates studied in this work.
- Full Text:
- Date Issued: 2017
Investigation of photophysicochemical properties of zinc phthalocyanines conjugated to metallic nanoparticles
- Dube, Edith, Nwaji, Njemuwa, Oluwole, David O, Mack, John, Nyokong, Tebello
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
- Authors: Dube, Edith , Nwaji, Njemuwa , Oluwole, David O , Mack, John , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233425 , vital:50089 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.09.020"
- Description: The syntheses of zinc(II) tetra–[3–(4–phenoxy) (propanoic acid) phthalocyanine] (2) and zinc(II) mono–[3–(4–phenoxy) (propanoic acid) phthalocyanine (3) are reported in this work. Compounds 2 and 3 were covalently linked to glutathione capped silver (AgNPs–GSH), gold (AuNPs–GSH) and silver-gold alloy (Ag3Au1NPs–GSH) nanoparticles (NPs) via an amide bond formation to afford the conjugates: 2–AgNPs–GSH, 3–AgNPs–GSH, 2–AuNPs–GSH, 3–AuNPs–GSH, 2-Ag3Au1NPs–GSH and 3-Ag3Au1NPs–GSH. The photophysicochemical behaviours of the compounds and their conjugates with NPs were assessed in solution. The conjugates afforded a decrease in fluorescence quantum yields and lifetimes with improved triplet quantum yields in comparison to the compounds. Accordingly, the AgNPs and AuNPs conjugates with the compounds afforded high singlet quantum yields. On the contrary, the conjugates of the alloy afforded decreased singlet quantum yields probably due to the screening effect. The compounds and their conjugates with NPs could serve as a viable and efficacious photosensitizer for photodynamic therapy.
- Full Text:
- Date Issued: 2017
Nonlinear optical dynamics of benzothiazole derivatized phthalocyanines in solution, thin films and when conjugated to nanoparticles
- Nwaji, Njemuwa, Jones, Benjamin, Mack, John, Oluwole, David O, Nyokong, Tebello
- Authors: Nwaji, Njemuwa , Jones, Benjamin , Mack, John , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190426 , vital:44993 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.05.042"
- Description: Benzothiazole phthalocynines complexes: tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] indium(III) chloride (1) and tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] indium(III) chloride (2) were synthesisized and their nanosecond nonlinear optical behaviours in solution, solid state and when conjugated to metallic nanoparticles were examined and compared to those of the corresponding ZnPc and GaPc which are designated as: tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] zinc(II) (3), tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5) and tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6). Trends in the electronic structures were identified through a comparison of the UV–vis absorption and magnetic circular dichroism (MCD) spectroscopy of the complexes and calculated spectra predicted by time dependent density functional theory (TD-DFT). Of all the complexes and nanoconjugates, complex 2 (containing sulphur linkages and In as a central metal) gave the best optical limiting behaviour.
- Full Text:
- Date Issued: 2017
- Authors: Nwaji, Njemuwa , Jones, Benjamin , Mack, John , Oluwole, David O , Nyokong, Tebello
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190426 , vital:44993 , xlink:href="https://doi.org/10.1016/j.jphotochem.2017.05.042"
- Description: Benzothiazole phthalocynines complexes: tetrakis[(benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] indium(III) chloride (1) and tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] indium(III) chloride (2) were synthesisized and their nanosecond nonlinear optical behaviours in solution, solid state and when conjugated to metallic nanoparticles were examined and compared to those of the corresponding ZnPc and GaPc which are designated as: tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] zinc(II) (3), tetrakis[(4-benzo[d]thiazol-2-ylphenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5) and tetrakis[(4-benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6). Trends in the electronic structures were identified through a comparison of the UV–vis absorption and magnetic circular dichroism (MCD) spectroscopy of the complexes and calculated spectra predicted by time dependent density functional theory (TD-DFT). Of all the complexes and nanoconjugates, complex 2 (containing sulphur linkages and In as a central metal) gave the best optical limiting behaviour.
- Full Text:
- Date Issued: 2017
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