Spectrophotometric and electrochemical studies of the interaction between iron (II) tetrasulfophthalocyanine and histamine
- Oni, Joshua, Nyokong, Tebello
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289629 , vital:56657 , xlink:href="https://doi.org/10.1142/S1088424602000233"
- Description: The interaction between iron(II) tetrasulfophthalocyanine ([FeIITSPc]4+) and histamine results in the oxidation of the central metal by oxygen in the former, with the formation of a complex denoted as [(His)FeIIITSPc]3− (where His = histamine). The rate constant for the formation of the complex is kf = 2.41 × 10−2dm3.mol−1.s−1 and an equilibrium constant of 6.3 dm3.mol-1 was obtained. The oxidation state of the central metal of [FeIITSPc]4− before and after the coordination of histamine is confirmed by spectroelectrochemistry. Further electrochemical oxidation of this [(His)FeIIITsPc]3− derivative results in a metal-based process proposed to involve an FeIV phthalocyanine species.
- Full Text:
- Date Issued: 2002
- Authors: Oni, Joshua , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289629 , vital:56657 , xlink:href="https://doi.org/10.1142/S1088424602000233"
- Description: The interaction between iron(II) tetrasulfophthalocyanine ([FeIITSPc]4+) and histamine results in the oxidation of the central metal by oxygen in the former, with the formation of a complex denoted as [(His)FeIIITSPc]3− (where His = histamine). The rate constant for the formation of the complex is kf = 2.41 × 10−2dm3.mol−1.s−1 and an equilibrium constant of 6.3 dm3.mol-1 was obtained. The oxidation state of the central metal of [FeIITSPc]4− before and after the coordination of histamine is confirmed by spectroelectrochemistry. Further electrochemical oxidation of this [(His)FeIIITsPc]3− derivative results in a metal-based process proposed to involve an FeIV phthalocyanine species.
- Full Text:
- Date Issued: 2002
Synthesis, photophysical and photochemical studies of germanium and tin phthalocyanine complexes
- Maree, Suzanne, Phillips, David, Nyokong, Tebello
- Authors: Maree, Suzanne , Phillips, David , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289667 , vital:56661 , xlink:href="https://doi.org/10.1142/S108842460200004X"
- Description: This work reports on the synthesis of tin and germanium phthalocyanine complexes containing phenoxy and substituted phenoxy groups as phthalocyanine ring substituents. The compounds studied are: dichlorogermanium phthalocyanine complexes containing eight phenoxy (4a), o-methyl phenoxy (4b) or estrone (4c) groups on the ring. The corresponding dichlorotin complexes (5a, 5b and 5c) and diiodotin complex (6a) were also investigated, as well as diestrone phthalocyaninato tin (7). Germanium octaphenoxy phthalocyanine complexes undergo phototransformation rather than direct photobleaching, whereas tin octaphenoxy phthalocyanine complexes undergo a photobleaching process, which is mediated by photoreduction of the phthalocyanine ring. Tin octaphenoxy phthalocyanine complexes gave higher ΦΔ values than the corresponding germanium complexes. Also tin phthalocyanine complexes containing an unsubstituted ring gave higher ΦΔ values than the corresponding octaphenoxy substituted complexes. The triplet quantum yields increased with the increase in electron-donating power of the ring substituents.
- Full Text:
- Date Issued: 2002
- Authors: Maree, Suzanne , Phillips, David , Nyokong, Tebello
- Date: 2002
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/289667 , vital:56661 , xlink:href="https://doi.org/10.1142/S108842460200004X"
- Description: This work reports on the synthesis of tin and germanium phthalocyanine complexes containing phenoxy and substituted phenoxy groups as phthalocyanine ring substituents. The compounds studied are: dichlorogermanium phthalocyanine complexes containing eight phenoxy (4a), o-methyl phenoxy (4b) or estrone (4c) groups on the ring. The corresponding dichlorotin complexes (5a, 5b and 5c) and diiodotin complex (6a) were also investigated, as well as diestrone phthalocyaninato tin (7). Germanium octaphenoxy phthalocyanine complexes undergo phototransformation rather than direct photobleaching, whereas tin octaphenoxy phthalocyanine complexes undergo a photobleaching process, which is mediated by photoreduction of the phthalocyanine ring. Tin octaphenoxy phthalocyanine complexes gave higher ΦΔ values than the corresponding germanium complexes. Also tin phthalocyanine complexes containing an unsubstituted ring gave higher ΦΔ values than the corresponding octaphenoxy substituted complexes. The triplet quantum yields increased with the increase in electron-donating power of the ring substituents.
- Full Text:
- Date Issued: 2002
Spectroscopic studies of the interaction of cobalt (II) N, N', N ″, N‴-tetramethyltetra-3, 4-pyridinoporphyrazine with amino acids and nitrogen oxides
- Thamae, Mamothibe A, Nyokong, Tebello
- Authors: Thamae, Mamothibe A , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291617 , vital:56892 , xlink:href="https://doi.org/10.1002/jpp.551"
- Description: The interaction of histidine, cysteine, NO and nitrite with cobalt(II) N,N',N″,N‴-tetramethyltetra-3,4-tetrapyridinoporphyrazine ([CoIItmtppa]4+) is reported. Metal-based autoreduction of [CoIItmtppa]4+ occurs with the formation of the [CoItmtppa(-2)]3+ species in the presence of histidine and cysteine. Kinetic data for the auto reduction of [CoIItmtppa]4+ in the presence of these amino acids gave the rate constants kf = 2.1 × 101 and 2.8 dm3 mol-1 s-1, for cysteine and histidine, respectively. One molecule of NO or nitrite was found to coordinate to the [CoIItmtppa]4+ species. The equilibrium and rate constants for the coordination of the nitric oxide were K = 2.3 × 104dm3mol-1 and kf = 7.5 dm3mol-1s-1, respectively. The coordination of nitrite to [CoIItmtppa]4+ occurred with an equilibrium constant of K = 2.0 × 102dm3mol-1 and a rate constant of kf = 4.0 × 10-3dm3mol-1s-1. There was no evidence for the coordination of two molecules of nitrite to the [CoIItmtppa]4+ species.
- Full Text:
- Date Issued: 2001
- Authors: Thamae, Mamothibe A , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/291617 , vital:56892 , xlink:href="https://doi.org/10.1002/jpp.551"
- Description: The interaction of histidine, cysteine, NO and nitrite with cobalt(II) N,N',N″,N‴-tetramethyltetra-3,4-tetrapyridinoporphyrazine ([CoIItmtppa]4+) is reported. Metal-based autoreduction of [CoIItmtppa]4+ occurs with the formation of the [CoItmtppa(-2)]3+ species in the presence of histidine and cysteine. Kinetic data for the auto reduction of [CoIItmtppa]4+ in the presence of these amino acids gave the rate constants kf = 2.1 × 101 and 2.8 dm3 mol-1 s-1, for cysteine and histidine, respectively. One molecule of NO or nitrite was found to coordinate to the [CoIItmtppa]4+ species. The equilibrium and rate constants for the coordination of the nitric oxide were K = 2.3 × 104dm3mol-1 and kf = 7.5 dm3mol-1s-1, respectively. The coordination of nitrite to [CoIItmtppa]4+ occurred with an equilibrium constant of K = 2.0 × 102dm3mol-1 and a rate constant of kf = 4.0 × 10-3dm3mol-1s-1. There was no evidence for the coordination of two molecules of nitrite to the [CoIItmtppa]4+ species.
- Full Text:
- Date Issued: 2001
Syntheses and photochemical properties of octasubstituted phthalocyaninato zinc complexes
- Maree, Suzanne, Nyokong, Tebello
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304841 , vital:58495 , xlink:href="https://doi.org/10.1002/jpp.388"
- Description: In this work a selection of octasubstituted phthalocyaninato zinc complexes were synthesized and their photochemistry studied. The substituents included cholesterol (3a), estrone (3b), naphthol (3c) and phenoxy groups substituted with CH3 (3d), C(CH3)3 (at two positions, 3e), C(CH3)3 (3f), NO2 (3g), NH2 (3h), COH (3i), COOH (3j), and H (3k). In general, complexes containing electron-donating groups attached to the phenoxy ring (e.g. 3e and 3f) were found to be photochemically unstable with photobleaching quantum yields of the order of 10−3. In the presence of electron-withdrawing groups (3g, 3i, and 3j) the photobleaching quantum yields were of the order of 10−6 to 10−5. Singlet oxygen quantum yields (ΦΔ) ranged from 0.01 to 0.73. The lowest ΦΔ was observed for the highly aggregated complex 3c. All the complexes showed aggregation at high concentrations. Electrochemical reduction using a thin-layer spectroelectrochemistry cell showed that the complexes become more monomeric following reduction.
- Full Text:
- Date Issued: 2001
- Authors: Maree, Suzanne , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304841 , vital:58495 , xlink:href="https://doi.org/10.1002/jpp.388"
- Description: In this work a selection of octasubstituted phthalocyaninato zinc complexes were synthesized and their photochemistry studied. The substituents included cholesterol (3a), estrone (3b), naphthol (3c) and phenoxy groups substituted with CH3 (3d), C(CH3)3 (at two positions, 3e), C(CH3)3 (3f), NO2 (3g), NH2 (3h), COH (3i), COOH (3j), and H (3k). In general, complexes containing electron-donating groups attached to the phenoxy ring (e.g. 3e and 3f) were found to be photochemically unstable with photobleaching quantum yields of the order of 10−3. In the presence of electron-withdrawing groups (3g, 3i, and 3j) the photobleaching quantum yields were of the order of 10−6 to 10−5. Singlet oxygen quantum yields (ΦΔ) ranged from 0.01 to 0.73. The lowest ΦΔ was observed for the highly aggregated complex 3c. All the complexes showed aggregation at high concentrations. Electrochemical reduction using a thin-layer spectroelectrochemistry cell showed that the complexes become more monomeric following reduction.
- Full Text:
- Date Issued: 2001
Synthesis, spectroscopy and electrochemistry of octaphenoxyphthalocyaninato silicon complexes
- Maree, M David, Nyokong, Tebello
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304863 , vital:58497 , xlink:href="https://doi.org/10.1002/jpp.361"
- Description: A number of octaphenoxyphthalocyaninato silicon complexes containing a variety of axial ligands, represented by (OPh)8PcSi(X)2 (where X = chloro 3, hydroxy 4, (4-carboxybenzene) acetato 5, isonicatinato 6, propionato 7, nitrophenoxy 8 and dimethylaminoxy 9) have been synthesized using a convenient route starting with the 4,5-diphenoxy-1,2-dicyanobenzene. 1H NMR and UV/vis spectra, and the cyclic voltammetry of the complexes are reported. The complexes are obtained in high yield and are soluble in many organic solvents. Cyclic voltammetry revealed two reduction couples and one oxidation couple for these complexes. Analysis of the cyclic voltammograms showed that compounds 6 and 8 were easier to oxidize and more difficult to reduce than the rest. Also cyclic voltammetry data suggested that electron transfer was not governed only by diffusion.
- Full Text:
- Date Issued: 2001
- Authors: Maree, M David , Nyokong, Tebello
- Date: 2001
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/304863 , vital:58497 , xlink:href="https://doi.org/10.1002/jpp.361"
- Description: A number of octaphenoxyphthalocyaninato silicon complexes containing a variety of axial ligands, represented by (OPh)8PcSi(X)2 (where X = chloro 3, hydroxy 4, (4-carboxybenzene) acetato 5, isonicatinato 6, propionato 7, nitrophenoxy 8 and dimethylaminoxy 9) have been synthesized using a convenient route starting with the 4,5-diphenoxy-1,2-dicyanobenzene. 1H NMR and UV/vis spectra, and the cyclic voltammetry of the complexes are reported. The complexes are obtained in high yield and are soluble in many organic solvents. Cyclic voltammetry revealed two reduction couples and one oxidation couple for these complexes. Analysis of the cyclic voltammograms showed that compounds 6 and 8 were easier to oxidize and more difficult to reduce than the rest. Also cyclic voltammetry data suggested that electron transfer was not governed only by diffusion.
- Full Text:
- Date Issued: 2001
Facile synthesis, spectroscopic and electrochemical properties, and theoretical calculations of porphyrin dimers with a bridging amide-bonded xanthene moiety
- Liang, Xu, Xu, Li, Li, Minzhi, Mack, John, Stone, Justin, Nyokong, Tebello, Jiang, Yu, Kobayashi, Nagao, Zhu, Weihua
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Language: English
- Type: Article
- Identifier: vital:7292 , http://hdl.handle.net/10962/d1020355
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety. , Original publication is available at http://dx.doi.org/10.1142/S1088424615500492
- Full Text: false
- Authors: Liang, Xu , Xu, Li , Li, Minzhi , Mack, John , Stone, Justin , Nyokong, Tebello , Jiang, Yu , Kobayashi, Nagao , Zhu, Weihua
- Language: English
- Type: Article
- Identifier: vital:7292 , http://hdl.handle.net/10962/d1020355
- Description: A free base porphyrin dimer bridged by a flexible amide-bonded xanthene moiety and its binuclear zinc(II) complex zinc(II) complex were synthesized and characterized. Structural characterization by MS and 1H NMR spectroscopy confirmed the bridged porphyrin dimer structure. The properties of the dimers were characterized by IR, UV-visible absorption, fluorescence and magnetic circular dichroism (MCD) spectroscopy, and electrochemistry studies. Theoretical calculations were carried out to analyze the electronic structures of porphyrin dimers with a bridging amide-bonded xanthene moiety. , Original publication is available at http://dx.doi.org/10.1142/S1088424615500492
- Full Text: false
Optical properties and electronic structures of axially-ligated group 9 porphyrins
- Wang, Bei-Bei, Zuo, Huiping, Mack, John, Majumdar, Poulomi, Nyokong, Tebello, Chan, Kin Shing, Shen, Zhen
- Authors: Wang, Bei-Bei , Zuo, Huiping , Mack, John , Majumdar, Poulomi , Nyokong, Tebello , Chan, Kin Shing , Shen, Zhen
- Language: English
- Type: Article
- Identifier: vital:7295 , http://hdl.handle.net/10962/d1020358
- Description: A series of group 9 metal tetra-(p-tolyl)-porphyrin (M(ttp), M = Co(II), Rh(III), Ir(III)) complexes with axial phenyl substituents have been synthesized and characterized. An aryl bromide cleavage reaction of transition metal complexes was used to prepare the complexes from Co(ttp), Rh(ttp)Cl and Ir(ttp)COCl, respectively. Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations have been used to study trends in the optical spectra and electronic structures. The effect of introducing different para-substituents on the phenyl substituents was examined. During fluorescence emission studies, phosphorescence was observed for the Ir(III) complexes in the near infrared (NIR) region. , Original publication is available at http://dx.doi.org/10.1142/S108842461550073X
- Full Text: false
- Authors: Wang, Bei-Bei , Zuo, Huiping , Mack, John , Majumdar, Poulomi , Nyokong, Tebello , Chan, Kin Shing , Shen, Zhen
- Language: English
- Type: Article
- Identifier: vital:7295 , http://hdl.handle.net/10962/d1020358
- Description: A series of group 9 metal tetra-(p-tolyl)-porphyrin (M(ttp), M = Co(II), Rh(III), Ir(III)) complexes with axial phenyl substituents have been synthesized and characterized. An aryl bromide cleavage reaction of transition metal complexes was used to prepare the complexes from Co(ttp), Rh(ttp)Cl and Ir(ttp)COCl, respectively. Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations have been used to study trends in the optical spectra and electronic structures. The effect of introducing different para-substituents on the phenyl substituents was examined. During fluorescence emission studies, phosphorescence was observed for the Ir(III) complexes in the near infrared (NIR) region. , Original publication is available at http://dx.doi.org/10.1142/S108842461550073X
- Full Text: false