Porphyrin dimers with a bridging chiral amide-bonded benzo-moiety
- Liang, Xu, Qin, Mingfeng, Zhou, Lin, Liu, Tingting, Li, Minzhi, Mack, John, Ndebele, Nobuhle, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
- Full Text:
- Date Issued: 2018
- Authors: Liang, Xu , Qin, Mingfeng , Zhou, Lin , Liu, Tingting , Li, Minzhi , Mack, John , Ndebele, Nobuhle , Nyokong, Tebello , Zhu, Weihua
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233433 , vital:50090 , xlink:href="https://doi.org/10.1016/j.dyepig.2018.02.043"
- Description: The facile synthesis and characterization of four porphyrin dimers which introduced stereomeric centers with chiral amide-bonded para- and meta-disubstituted benzo-moiety is reported. Trends in the electronic structures and optical and redox properties are analyzed through a comparison with theoretical calculations to explore the effect of positional isomerism of the bridging benzene rings.
- Full Text:
- Date Issued: 2018
Positively charged styryl pyridine substituted Zn (II) Phthalocyanines for Photodynamic Therapy and Photoantimicrobial Chemotherapy
- Magadla, Aviwe, Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Magadla, Aviwe , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190600 , vital:45009 , xlink:href="https://doi.org/10.1039/D1DT01047F"
- Description: Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(II) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(II) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(II) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.
- Full Text:
- Date Issued: 2021
- Authors: Magadla, Aviwe , Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190600 , vital:45009 , xlink:href="https://doi.org/10.1039/D1DT01047F"
- Description: Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(II) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(II) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(II) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.
- Full Text:
- Date Issued: 2021
Preparation of NIR absorbing axial substituted tin (iv) porphyrins and their photocytotoxic properties
- Babu, Balaji, Amuhaya, Edith K, Oluwole, David O, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
- Full Text:
- Date Issued: 2019
- Authors: Babu, Balaji , Amuhaya, Edith K , Oluwole, David O , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/234592 , vital:50211 , xlink:href="https://doi.org/10.1039/C8MD00373D"
- Description: Sn(IV) porphyrins ([Sn(IV)TTP(3PyO)2] (5) and [Sn(IV)TPP(3PyO)2] (6) [tetrathienylporphyrin (TTP), tetraphenylporphyrin (TPP), and pyridyloxy (PyO)]) were prepared and characterized and their photocytotoxicity upon irradiation with 625 nm light has been studied. The presence of the 3PyO axial ligands was found to limit the aggregation and enhance the solubility of 5 and 6 in DMF/H2O (1 : 1). The photophysical properties and photodynamic therapy (PDT) activity of the meso-2-thienyl and meso-phenyl-substituted Sn(IV) porphyrins are compared. 5 and 6 were found to be photocytotoxic in MCF-7 cancer cells when irradiated with a Thorlabs M625L3 LED at 625 nm but remained nontoxic in the dark. The PDT activity of Sn(IV) meso-tetra-2-thienylporphyrin 5 was found to be significantly enhanced relative to its analogous tetraphenylporphyrin 6. There is a marked red-shift of the Q00 band of 5 into the therapeutic window due to the meso-2-thienyl rings, and 5 has an unusually high singlet oxygen quantum yield value of 0.83 in DMF. The results demonstrate that readily synthesized axially ligated Sn(IV) meso-arylporphyrins are potentially suitable for use as singlet oxygen photosensitizers in biomedical applications and merit further in depth investigation in this context.
- Full Text:
- Date Issued: 2019
Promotion of Catalytic Oxygen Reduction Reactions
- Wei, Yuqin, Zhao, Long, Yuan, Rui, Xue, Zhaoli, Mack, John, Chivumba, Choonzo, Nyokong, Tebello, Zhang, Jianming
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
- Authors: Wei, Yuqin , Zhao, Long , Yuan, Rui , Xue, Zhaoli , Mack, John , Chivumba, Choonzo , Nyokong, Tebello , Zhang, Jianming
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/300347 , vital:57919 , xlink:href="https://doi.org/10.1021/acs.inorgchem.2c01591"
- Description: Three ABAB-type cobalt meso-tetraarylporphyrins with fluorine (F-CoPor), acetic acid (AC-CoPor), and cyanoacetic acid (CN-CoPor) groups at the para-positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the meso-aryl rings. Electrochemical measurements suggest that electrodes with CN-CoPor (CN-CoPor/C) exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the F-CoPor/C electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the meso-position is an efficient way to modify the ORR performance.
- Full Text:
- Date Issued: 2022
Push-pull type Co (III) corroles
- Niu, Yingjie, Zhu, Weihua, Mack, John, Dubazana, Nadine, Nyokong, Tebello, Fu, Bo, Xu, Haijun, Liang, Xu
- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
- Full Text:
- Date Issued: 2021
- Authors: Niu, Yingjie , Zhu, Weihua , Mack, John , Dubazana, Nadine , Nyokong, Tebello , Fu, Bo , Xu, Haijun , Liang, Xu
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190826 , vital:45032 , xlink:href="https://doi.org/10.1142/S1088424621500279"
- Description: The rational design and preparation of three A2B type Co(III)triarylcorroles with push- and pull-substituents are reported. The structure-property relationships were identified by comparing their optically spectroscopic and electrochemical properties to trends predicted in DFT and TD-DFT calculations. The results demonstrate that the Co(III)triarylcorroles are highly efficient catalysts for electrocatalyzed hydrogen evolutions (HERs) and oxygen reductions (ORRs), and that their reactivity can be modulated by changing the meso-B-substituent of the Co(III)Corroles.
- Full Text:
- Date Issued: 2021
Push–pull type manganese (III) corroles
- Liang, Xu, Fang, Junjia, Li, Minzhi, Chen, Qiuyun, Mack, John, Molupe, Nthabeleng, Nyokong, Tebello, Zhu, Weihua
- Authors: Liang, Xu , Fang, Junjia , Li, Minzhi , Chen, Qiuyun , Mack, John , Molupe, Nthabeleng , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189201 , vital:44826 , xlink:href="https://doi.org/10.1142/S1088424617500778"
- Description: The synthesis of three low symmetry A2B type Mn(III)triarylcorroles with meso-aryl substituents that provide push–pull electron-donating and -withdrawing properties is reported. An analysis of the structure-property relationships for the optical and redox properties has been carried out through a comparison with the results of theoretical calculations. The results demonstrate that A2B type Mn(III)triarylcorroles interact strongly with cell-free circulating tumor deoxyribonucleic acid (ctDNA) in solution, and that the interaction constants are enhanced when a stronger electron-donating substituent is introduced at the 10-position of the meso-triarylcorrole ligand.
- Full Text:
- Date Issued: 2017
- Authors: Liang, Xu , Fang, Junjia , Li, Minzhi , Chen, Qiuyun , Mack, John , Molupe, Nthabeleng , Nyokong, Tebello , Zhu, Weihua
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189201 , vital:44826 , xlink:href="https://doi.org/10.1142/S1088424617500778"
- Description: The synthesis of three low symmetry A2B type Mn(III)triarylcorroles with meso-aryl substituents that provide push–pull electron-donating and -withdrawing properties is reported. An analysis of the structure-property relationships for the optical and redox properties has been carried out through a comparison with the results of theoretical calculations. The results demonstrate that A2B type Mn(III)triarylcorroles interact strongly with cell-free circulating tumor deoxyribonucleic acid (ctDNA) in solution, and that the interaction constants are enhanced when a stronger electron-donating substituent is introduced at the 10-position of the meso-triarylcorrole ligand.
- Full Text:
- Date Issued: 2017
Pyridone substituted phthalocyanines: Photophysico-chemical properties and TD-DFT calculations
- Abdurrahmanoğlu, Şaziye, Canlica, Mevlüde, Mack, John, Nyokong, Tebello
- Authors: Abdurrahmanoğlu, Şaziye , Canlica, Mevlüde , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188216 , vital:44735 , xlink:href="https://doi.org/10.1142/S1088424617500730"
- Description: 4-(6-methyl-3-nitro-2-oxo-1,2-dihydropyridin-4-yloxy)phthalonitrile has been used to prepare a novel Zn(II) phthalocyanines with four peripheral pyridone substituents. The compound has been characterized by UV-visible absorption, FT-IR and 11H-NMR spectroscopy, elemental analysis and MALDI-TOF mass spectroscopy. The fluorescence, triplet quantum and singlet oxygen quantum yields have been determined and TD-DFT calculations have been used to identify trends in the electronic structure.
- Full Text:
- Date Issued: 2018
- Authors: Abdurrahmanoğlu, Şaziye , Canlica, Mevlüde , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188216 , vital:44735 , xlink:href="https://doi.org/10.1142/S1088424617500730"
- Description: 4-(6-methyl-3-nitro-2-oxo-1,2-dihydropyridin-4-yloxy)phthalonitrile has been used to prepare a novel Zn(II) phthalocyanines with four peripheral pyridone substituents. The compound has been characterized by UV-visible absorption, FT-IR and 11H-NMR spectroscopy, elemental analysis and MALDI-TOF mass spectroscopy. The fluorescence, triplet quantum and singlet oxygen quantum yields have been determined and TD-DFT calculations have been used to identify trends in the electronic structure.
- Full Text:
- Date Issued: 2018
Singly and Doubly N-Confused Calix [4] phyrin Organoplatinum (II) Complexes as Near-IR Triplet Sensitizers
- Pushpanandan, Poornenth, Maurya, Yogesh Kumar, Omagari, Toshihiro, Hirosawa, Ryuji, Ishida, Masatoshi, Mori, Shigeki, Yasutake, Yuhsuke, Fukatsu, Susumu, Mack, John, Nyokong, Tebello, Furuta, Hiroyuki
- Authors: Pushpanandan, Poornenth , Maurya, Yogesh Kumar , Omagari, Toshihiro , Hirosawa, Ryuji , Ishida, Masatoshi , Mori, Shigeki , Yasutake, Yuhsuke , Fukatsu, Susumu , Mack, John , Nyokong, Tebello , Furuta, Hiroyuki
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233144 , vital:50061 , xlink:href="https://doi.org/10.1021/acs.inorgchem.7b02047"
- Description: Organoplatinum(II) complexes of calix[4]phyrin analogues, singly N-confused calix[4]phyrin (Pt-2), and doubly N-confused calix[4]phyrin (Pt-3), were synthesized and characterized. The explicit structures of these organoplatinum(II) complexes were elucidated by single-crystal X-ray diffraction and spectroscopic studies. The introduction of N-confused pyrrole rings to the parent calix[4]phyrin scaffold was found to have profound effects on the photophysical properties, such as the bathochromic shifts of both the absorption and phosphorescence maxima. The triplet excited state properties of these platinum complexes were analyzed by DFT calculations at the B3LYP level. The organoplatinum(II) complexes derived from the deformed scaffolds can serve as potent triplet sensitizers for singlet oxygen generation under aerobic conditions.
- Full Text:
- Date Issued: 2017
- Authors: Pushpanandan, Poornenth , Maurya, Yogesh Kumar , Omagari, Toshihiro , Hirosawa, Ryuji , Ishida, Masatoshi , Mori, Shigeki , Yasutake, Yuhsuke , Fukatsu, Susumu , Mack, John , Nyokong, Tebello , Furuta, Hiroyuki
- Date: 2017
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233144 , vital:50061 , xlink:href="https://doi.org/10.1021/acs.inorgchem.7b02047"
- Description: Organoplatinum(II) complexes of calix[4]phyrin analogues, singly N-confused calix[4]phyrin (Pt-2), and doubly N-confused calix[4]phyrin (Pt-3), were synthesized and characterized. The explicit structures of these organoplatinum(II) complexes were elucidated by single-crystal X-ray diffraction and spectroscopic studies. The introduction of N-confused pyrrole rings to the parent calix[4]phyrin scaffold was found to have profound effects on the photophysical properties, such as the bathochromic shifts of both the absorption and phosphorescence maxima. The triplet excited state properties of these platinum complexes were analyzed by DFT calculations at the B3LYP level. The organoplatinum(II) complexes derived from the deformed scaffolds can serve as potent triplet sensitizers for singlet oxygen generation under aerobic conditions.
- Full Text:
- Date Issued: 2017
Sn (iv) N-confused porphyrins as photosensitizer dyes for photodynamic therapy in the near IR region
- Babu, Balaji, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186648 , vital:44521 , xlink:href="https://doi.org/10.1039/D0DT03296D"
- Description: The utility of Sn(IV) N-confused porphyrin (SnNCP) for use as photosensitizer dyes in photodynamic therapy is investigated. SnNCP has an unusually high singlet oxygen quantum yield of 0.72 in DMSO. IC50 values of 1.6 and 12.8 μM were obtained against MCF-7 cells upon irradiation with 660 and 780 nm LEDs.
- Full Text:
- Date Issued: 2020
Sn (iv) N-confused porphyrins as photosensitizer dyes for photodynamic therapy in the near IR region
- Authors: Babu, Balaji , Mack, John , Nyokong, Tebello
- Date: 2020
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186648 , vital:44521 , xlink:href="https://doi.org/10.1039/D0DT03296D"
- Description: The utility of Sn(IV) N-confused porphyrin (SnNCP) for use as photosensitizer dyes in photodynamic therapy is investigated. SnNCP has an unusually high singlet oxygen quantum yield of 0.72 in DMSO. IC50 values of 1.6 and 12.8 μM were obtained against MCF-7 cells upon irradiation with 660 and 780 nm LEDs.
- Full Text:
- Date Issued: 2020
Solar Driven Photocatalytic Activity of Porphyrin Sensitized TiO2
- Otieno, Sebastien, Lanterna, Anabel E, Mack, John, Derese, Solomon, Amuhaya, Edith K, Nyokong, Tebello, Scaiano, Juan C
- Authors: Otieno, Sebastien , Lanterna, Anabel E , Mack, John , Derese, Solomon , Amuhaya, Edith K , Nyokong, Tebello , Scaiano, Juan C
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190612 , vital:45010 , xlink:href="https://doi.org/10.3390/molecules26113131"
- Description: The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2 ) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
- Full Text:
- Date Issued: 2021
- Authors: Otieno, Sebastien , Lanterna, Anabel E , Mack, John , Derese, Solomon , Amuhaya, Edith K , Nyokong, Tebello , Scaiano, Juan C
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190612 , vital:45010 , xlink:href="https://doi.org/10.3390/molecules26113131"
- Description: The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2 ) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.
- Full Text:
- Date Issued: 2021
Spectroscopic and nonlinear optical properties of the four positional isomers of 4α-(4-tert-butylphenoxy) phthalocyanine
- Ngubeni, Grace N, Britton, Jonathan, Mack, John, New, Edward, Hancox, Ian, Walker, Marc, Nyokong, Tebello, Jones, Tim S, Khene,Samson M
- Authors: Ngubeni, Grace N , Britton, Jonathan , Mack, John , New, Edward , Hancox, Ian , Walker, Marc , Nyokong, Tebello , Jones, Tim S , Khene,Samson M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241448 , vital:50940 , xlink:href="https://doi.org/10.1039/C5TC01601K"
- Description: The spectroscopic and nonlinear optical properties of the positional isomers of metal free 4α-(4-tert-butylphenoxy) phthalocyanine are presented. Second order nonlinear polarizability (β), imaginary hyperpolarizability (Im(γ)) and imaginary susceptibility (Im[χ(3)]) values were determined for the four positional isomers. The measured β values of the four isomers displayed the following trend, C4h (34.0 × 10−5 m MW−1) > D2h (28.8 × 10−5 m MW−1) > C2v (22.8 × 10−5 m MW−1) > Cs (13.7 × 10−5 m MW−1).
- Full Text:
- Date Issued: 2015
- Authors: Ngubeni, Grace N , Britton, Jonathan , Mack, John , New, Edward , Hancox, Ian , Walker, Marc , Nyokong, Tebello , Jones, Tim S , Khene,Samson M
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241448 , vital:50940 , xlink:href="https://doi.org/10.1039/C5TC01601K"
- Description: The spectroscopic and nonlinear optical properties of the positional isomers of metal free 4α-(4-tert-butylphenoxy) phthalocyanine are presented. Second order nonlinear polarizability (β), imaginary hyperpolarizability (Im(γ)) and imaginary susceptibility (Im[χ(3)]) values were determined for the four positional isomers. The measured β values of the four isomers displayed the following trend, C4h (34.0 × 10−5 m MW−1) > D2h (28.8 × 10−5 m MW−1) > C2v (22.8 × 10−5 m MW−1) > Cs (13.7 × 10−5 m MW−1).
- Full Text:
- Date Issued: 2015
Spectroscopic investigations and theoretical calculations of DABCO induced xanthene bridged self-assembled zinc (II) porphyrin dimer
- Xu, Li, Huang, Tingting, Liang, Xu, Mack, John, Harris, Jessica, Nyokong, Tebello, Li, Minzhi, Zhu, Weihua
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
- Full Text:
- Date Issued: 2016
- Authors: Xu, Li , Huang, Tingting , Liang, Xu , Mack, John , Harris, Jessica , Nyokong, Tebello , Li, Minzhi , Zhu, Weihua
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240732 , vital:50866 , xlink:href="https://doi.org/10.1142/S1088424616500231"
- Description: An in-depth study of the electronic structure of a 1,4-diazabicyclo[2.2.2]octane (DABCO) induced molecular self-assembled xanthene-bridged and amide-bonded porphyrin dimer is reported. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are used to identify trends in the optical spectroscopic properties. B3LYP geometry optimization predicts the formation of an almost perfectly eclipsed structure with respect to the two porphyrin rings with the analogous pyrrole nitrogens separated by 7.7–8.1 Å. The observed distinctive derivative-shaped band morphology of the pseudo-Faraday-A11 terms in the MCD spectra has been used to identify the main electronic Q and B-bands and to validate the TD-DFT calculations. The absence of a discernible splitting of the redox steps or a quenching of the fluorescence demonstrates that there is no significant exciton coupling between the two porphyrin rings.
- Full Text:
- Date Issued: 2016
Structural modification of RhIIItriarylcorroles for enhanced electrocatalyzed hydrogen evolution reactions
- Zhu, Weihua, Li, Lihua, Wang, Yu, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Liang, Xu
- Authors: Zhu, Weihua , Li, Lihua , Wang, Yu , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229933 , vital:49724 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.110046"
- Description: A series of A3 type RhIIItriarylcorroles 2a-c with different meso-substituents with differing electron-donating and withdrawing properties and two A2B type RhIIItriarylcorroles 4a-b with meso-methylthiophenyls at the B position have been prepared and characterized. An analysis of structure-property relationships of 2a-c and 4a-b has been carried out by comparing the optical spectroscopy and electrochemistry of the dyes to trends predicted in DFT and TD-DFT calculations. Rational structural modification strategies that enhance the suitability of 2a-c for use as highly efficient catalysts for hydrogen evolution reactions on glassy carbon electrodes coated with 2a-c/reduced graphene oxide composites and of 4a-b in surface-modified Au electrodes are explored.
- Full Text:
- Date Issued: 2022
- Authors: Zhu, Weihua , Li, Lihua , Wang, Yu , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Liang, Xu
- Date: 2022
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/229933 , vital:49724 , xlink:href="https://doi.org/10.1016/j.dyepig.2021.110046"
- Description: A series of A3 type RhIIItriarylcorroles 2a-c with different meso-substituents with differing electron-donating and withdrawing properties and two A2B type RhIIItriarylcorroles 4a-b with meso-methylthiophenyls at the B position have been prepared and characterized. An analysis of structure-property relationships of 2a-c and 4a-b has been carried out by comparing the optical spectroscopy and electrochemistry of the dyes to trends predicted in DFT and TD-DFT calculations. Rational structural modification strategies that enhance the suitability of 2a-c for use as highly efficient catalysts for hydrogen evolution reactions on glassy carbon electrodes coated with 2a-c/reduced graphene oxide composites and of 4a-b in surface-modified Au electrodes are explored.
- Full Text:
- Date Issued: 2022
Synthesis and Photophysical Investigation of Tetraazaporphyrin Substituted with Aggregation‐Induced Emission (AIE) Active Moieties
- Tasso, Thiago T, Furuyama, Taniyuki, Mack, John, Nyokong, Tebello, Kobayashi, Nagao
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
- Authors: Tasso, Thiago T , Furuyama, Taniyuki , Mack, John , Nyokong, Tebello , Kobayashi, Nagao
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193553 , vital:45346 , xlink:href="https://doi.org/10.1002/ejic.201500726"
- Description: The synthesis and characterization of free-base and ZnII tetraazaporphyrins with tetraphenylethylene (TPE) or diphenylphenanthrene (DPP) moieties that are known to be aggregation-induced emission (AIE) active is reported. The optical spectra contain the characteristic Q and B absorption bands of Gouterman's four-orbital model and a broad envelope of weaker charge-transfer bands in the 450–600 nm region. The observed fluorescence emission lies beyond 670 nm and originates exclusively from the decay of the S1 state of the macrocycle, regardless of the excitation wavelength used. Theoretical calculations provide further evidence of strong electronic communication between the peripheral TPE or DPP moieties and the central ring. The ZnII complexes were found to have relatively high singlet-oxygen quantum yields.
- Full Text:
- Date Issued: 2015
Synthesis and photophysical properties of BODIPY-decorated graphene quantum dot–phthalocyanine conjugates
- Nwahara, Nnamdi, Nkhahle, Reitumetse, Ngoy, Bokolombe P, Mack, John, Nyokong, Tebello
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
- Authors: Nwahara, Nnamdi , Nkhahle, Reitumetse , Ngoy, Bokolombe P , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/233409 , vital:50088 , xlink:href="https://doi.org/10.1039/C8NJ00758F"
- Description: This work reports on the synthesis and characterisation of novel supramolecular hybrids containing BODIPY-decorated graphene quantum dots (BODIPY@GQDs) and zinc phthalocyanine. Graphene quantum dots (GQDs) were functionalized with L-glutathione (GSH) in order to assist coupling to the BODIPY dye. {2,9(10)16(17)23(24)-Tetrakis-[3-(diethylamino)phenoxy]phthalocyaninato}zinc(II) (1) was immobilized via π–π stacking interaction on the BODIPY-decorated GQDs and pristine GQDs to form the supramolecular hybrids 1-BODIPY@GQDs and 1-GQDs, respectively. The photophysical and photochemical properties of these conjugates were investigated. Energy transfer occurred from the (i) GQDs to BODIPY, (ii) GQDs to 1, and (iii) BODIPY@GQDs to 1via fluorescence resonance energy transfer (FRET). The highest FRET efficiency was observed for the BODIPY@GQDs (0.93). The introduction of the BODIPY core to the GQD structure resulted in higher triplet, and singlet oxygen quantum yields for the resultant Pc/GQD hybrid (1-BODIPY@GQDs). The zeta potential values obtained imply a high colloidal stability for the supramolecular hybrids. The results suggest that such hybrids may be applied in fields such as photodynamic therapy (PDT), where a high singlet oxygen quantum yield is desired.
- Full Text:
- Date Issued: 2018
Synthesis and photophysical properties of covalent conjugates of aqua platinum (II) and octacarboxy-substituted zinc phthalocyanine
- Bulgakov, Roman A, Kuznetsova, Nina A, Dolotova, Olga V, Solovieva, Ludmila I, Mack, John, Chidawanyika, Wadzanai J U, Kaliya, Oleg L, Nyokong, Tebello
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
- Authors: Bulgakov, Roman A , Kuznetsova, Nina A , Dolotova, Olga V , Solovieva, Ludmila I , Mack, John , Chidawanyika, Wadzanai J U , Kaliya, Oleg L , Nyokong, Tebello
- Date: 2012
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/242726 , vital:51073 , xlink:href="https://doi.org/10.1142/S1088424612501209"
- Description: New covalent conjugates of aqua platinum(II) and octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum moieties on the periphery of the Pc ligand have been synthesized and characterized. The effect of the stepwise introduction of the aqua platinums on the photophysical and photochemical properties of these compounds has been investigated in dimethylsulfoxide solution. It has been found that aqua platinum moieties have only a limited effect on the dynamics of the singlet and triplet excited states, on the ability to sensitize singlet oxygen formation and on the photostability. Each conjugate has a high singlet oxygen quantum yield (ΦΔ 0.51–0.62) and thus retains potential for use as a dual action anticancer drugs by acting as a sensitizer for PDT in addition to the likely chemotherapeutic effects of the Pt(II) complexes.
- Full Text:
- Date Issued: 2012
Synthesis and photophysicochemical properties of BODIPY dye functionalized gold nanorods for use in antimicrobial photodynamic therapy
- Kubheka, Gugu, Uddin, Imran, Amuhaya, Edith K, Mack, John, Nyokong, Tebello
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith K , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
- Full Text:
- Date Issued: 2016
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith K , Mack, John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239897 , vital:50778 , xlink:href="https://doi.org/10.1142/S108842461650070X"
- Description: A series of boron dipyrromethene (BODIPY) dyes with properties that are ideal for a good photosensitizer have been prepared. Functionalization with bromine atoms and attachment to gold nanoparticles through a meso-aniline group results in high singlet oxygen quantum yields and low fluorescent quantum yields. Molecular modelling was used to analyze trends in the MO energies of various brominated aniline BODIPY dyes.
- Full Text:
- Date Issued: 2016
Synthesis and properties of chiral amide-bonded porphyrin dimers with various functional bridging blocks
- Zhu, Weihua, Haider, Syed Najeeb-uz-Zaman, Zhang, Honglin, Attatsi, Isaac K, Mack, John, Dingiswayo, Somila, Nyokong, Tebello, Song, Yuting, Xu, Haijun, Liang, Xu
- Authors: Zhu, Weihua , Haider, Syed Najeeb-uz-Zaman , Zhang, Honglin , Attatsi, Isaac K , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Song, Yuting , Xu, Haijun , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186791 , vital:44534 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107740"
- Description: Eight porphyrin dimers with various functional bridging blocks and chiral amide-bonds were synthesized and characterized. An analysis of the spectroscopy and electrochemistry has been carried out to demonstrate that the chiral properties can be modified by changing the interchromophoric through-space coupling distance between the two porphyrin chromophores by introducing various bonding and bridging blocks.
- Full Text:
- Date Issued: 2019
- Authors: Zhu, Weihua , Haider, Syed Najeeb-uz-Zaman , Zhang, Honglin , Attatsi, Isaac K , Mack, John , Dingiswayo, Somila , Nyokong, Tebello , Song, Yuting , Xu, Haijun , Liang, Xu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186791 , vital:44534 , xlink:href="https://doi.org/10.1016/j.dyepig.2019.107740"
- Description: Eight porphyrin dimers with various functional bridging blocks and chiral amide-bonds were synthesized and characterized. An analysis of the spectroscopy and electrochemistry has been carried out to demonstrate that the chiral properties can be modified by changing the interchromophoric through-space coupling distance between the two porphyrin chromophores by introducing various bonding and bridging blocks.
- Full Text:
- Date Issued: 2019
Synthesis, characterization and electrochemistry of rhodium (iii) complexes of meso-substituted [14] tribenzotriphyrin (2.1. 1)
- Xue, Zhaoli, Wang, Yemei, Mack, John, Mkhize, Scebi, Nyokong, Tebello, Fang, Yuanyuan, Ou, Zhongping, Kadish, Karl M
- Authors: Xue, Zhaoli , Wang, Yemei , Mack, John , Mkhize, Scebi , Nyokong, Tebello , Fang, Yuanyuan , Ou, Zhongping , Kadish, Karl M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241043 , vital:50899 , xlink:href="https://doi.org/10.1039/C6RA03028A"
- Description: A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a–d) with Rh2(C8H12)Cl2 provides RhIII–TriP complexes (2a–d) in 40−52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and 1H NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a–d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a–d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a–d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO–LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy π → π* transition of the [14]tribenzotriphyrin(2.1.1) π-system.
- Full Text:
- Date Issued: 2016
- Authors: Xue, Zhaoli , Wang, Yemei , Mack, John , Mkhize, Scebi , Nyokong, Tebello , Fang, Yuanyuan , Ou, Zhongping , Kadish, Karl M
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241043 , vital:50899 , xlink:href="https://doi.org/10.1039/C6RA03028A"
- Description: A thermal reaction using a series of [14]tribenzotriphyrins(2.1.1) (TriPs, 1a–d) with Rh2(C8H12)Cl2 provides RhIII–TriP complexes (2a–d) in 40−52% yields. The complexes were characterized by mass spectrometry, UV-visible absorption and 1H NMR spectroscopy. Single crystal X-ray analysis reveals that 2b adopts a dome-shaped conformation. The rhodium(III) ion is coordinated by the three pyrrole nitrogen atoms, two chloride ions and the nitrogen atom of an acetonitrile (CH3CN) solvent molecule. The optical spectra can be assigned using Michl's perimeter model. The L and B bands of the 2a–d complexes lie at ca. 600 and 500 nm, respectively, and are markedly red shifted relative to those of 1a–d. A reversible one-electron oxidation and two reversible one-electron reductions are observed in the cyclic voltammograms of 2a–d in CH2Cl2. The redox potentials are consistent with the optical data and the relatively narrow HOMO–LUMO gaps that are predicted in DFT calculations. TD-DFT calculations have been used to assign a third intense spectral band at 375 nm to a higher energy π → π* transition of the [14]tribenzotriphyrin(2.1.1) π-system.
- Full Text:
- Date Issued: 2016
Synthesis, characterization and photodynamic activity of Sn (iv) triarylcorroles with red-shifted Q bands
- Babu, Balaji, Prinsloo, Earl, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
- Full Text:
- Date Issued: 2019
- Authors: Babu, Balaji , Prinsloo, Earl , Mack, John , Nyokong, Tebello
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/187521 , vital:44668 , xlink:href="https://doi.org/10.1039/C9NJ03391B"
- Description: Two Sn(IV) triarylcorroles were synthesised and characterized. The absorption spectrum of a meso-thien-2-yl substituted tin(IV)corrole (1-Sn) is red shifted compared to its phenyl analogue (2-Sn) and shows no sign of aggregation in solution. 1-Sn and 2-Sn exhibited singlet oxygen quantum yields of 0.87 and 0.54 in DMF, and have a triplet lifetime of 31 and 50 μs, respectively. Time dependent cellular uptake in MCF-7 cells for 1-Sn reached a peak at 24 h, and 1-Sn was found to be more lipophilic than 2-Sn. 1-Sn showed good photo-cytotoxicity on exposure to a Thorlabs 625 nm LED with an IC50 value of 3.2 μM and remained inactive in the dark.
- Full Text:
- Date Issued: 2019