Fluorescence properties of alloyed ZnSeS quantum dots overcoated with ZnTe and ZnTe/ZnS shells
- Adegoke, Oluwasesan, Mashazi, Philani N, Nyokong, Tebello, Forbes, Patricia B C
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
- Full Text:
- Date Issued: 2016
- Authors: Adegoke, Oluwasesan , Mashazi, Philani N , Nyokong, Tebello , Forbes, Patricia B C
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240754 , vital:50868 , xlink:href="https://doi.org/10.1016/j.optmat.2016.02.024"
- Description: Fluorescent alloyed ternary ZnSeS quantum dots (QDs) have been synthesized via the pyrolysis of organometallic precursors. The effects of passivation of ZnTe and ZnTe/ZnS shells on the optical properties of the ternary alloyed ZnSeS core have been studied. A ligand exchange reaction using L-cysteine as a capping ligand was used to obtain water-soluble nanocrystals. The nanocrystals were each characterized by UV/vis absorption and fluorescence spectroscopy, transmission electron microscopy, X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) quantum yield (QY) of alloyed ZnSeS QDs was 14% and this value increased to 27% when ZnTe was overcoated around the surface but further coating with a ZnS shell decreased the PL QY slightly to 24%. This implies that ZnTe shell suppressed non-radiative recombination exciton states in the alloyed core while further layering with a ZnS shell offered no further improvement in suppressing the defect states. XPS analysis confirmed the presence of the first shell layering but showed a weakened intensity signal of S (2p) and Se (3d) for the ZnSeS/ZnTe/ZnS QDs. Our work demonstrates for the first time that shell passivation of alloyed Zn-based QDs can offer improved optical properties. We hope the optical information presented in this work will be useful in the selection of alloyed Zn-based QDs appropriate for the intended application.
- Full Text:
- Date Issued: 2016
Graphene quantum dots functionalized with 4-amino-2, 2, 6, 6-tetramethylpiperidine-N-oxide as fluorescence “turn-on” nanosensors
- Achadu, Ojodomo J, Britton, Jonathan, Nyokong, Tebello
- Authors: Achadu, Ojodomo J , Britton, Jonathan , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239854 , vital:50773 , xlink:href="https://doi.org/10.1007/s10895-016-1916-y"
- Description: In this study, we report on the fabrication of simple and rapid graphene quantum dots (GQDs)-based fluorescence “turn-ON” nanoprobes for sensitive and selective detection of ascorbic acid (AA). Pristine GQDs and S and N co-doped-GQDs (SN-GQDs) were functionalized with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4-amino-TEMPO, a nitroxide free radical). The nitroxide free radicals efficiently quenched the fluorescence of the GQDs and upon interaction of the nanoconjugates with ascorbic acid, the quenched fluorescence was restored. The linear ranges recorded were 0.5–5.7 μM and 0.1–5.5 μM for GQDs-4-amino-TEMPO and SN-GQDs-4amino-TEMPO nanoprobes, respectively. Limits of detection were found to be 60 nM and 84 nM for SN-GQDS-4-amino-TEMPO and GQDs-4-amino-TEMPO for AA detection, respectively. This novel fluorescence “turn-ON” technique showed to be highly rapid and selective towards AA detection.
- Full Text:
- Date Issued: 2016
- Authors: Achadu, Ojodomo J , Britton, Jonathan , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239854 , vital:50773 , xlink:href="https://doi.org/10.1007/s10895-016-1916-y"
- Description: In this study, we report on the fabrication of simple and rapid graphene quantum dots (GQDs)-based fluorescence “turn-ON” nanoprobes for sensitive and selective detection of ascorbic acid (AA). Pristine GQDs and S and N co-doped-GQDs (SN-GQDs) were functionalized with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxide (4-amino-TEMPO, a nitroxide free radical). The nitroxide free radicals efficiently quenched the fluorescence of the GQDs and upon interaction of the nanoconjugates with ascorbic acid, the quenched fluorescence was restored. The linear ranges recorded were 0.5–5.7 μM and 0.1–5.5 μM for GQDs-4-amino-TEMPO and SN-GQDs-4amino-TEMPO nanoprobes, respectively. Limits of detection were found to be 60 nM and 84 nM for SN-GQDS-4-amino-TEMPO and GQDs-4-amino-TEMPO for AA detection, respectively. This novel fluorescence “turn-ON” technique showed to be highly rapid and selective towards AA detection.
- Full Text:
- Date Issued: 2016
Improvement of nonlinear optical properties of phthalocyanine bearing diethyleneglycole chains
- Britton, Jonathan, Martynov, Alexander G, Oluwole, David O, Gorbunova, Yulia G, Tsivadze, Yulia G, Nyokong, Tebello
- Authors: Britton, Jonathan , Martynov, Alexander G , Oluwole, David O , Gorbunova, Yulia G , Tsivadze, Yulia G , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239812 , vital:50769 , xlink:href="https://doi.org/10.1142/S1088424616501042"
- Description: This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxyphthalocyanine 1H22 and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H22 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)χ(3)]/αα, βeffβeff, and γγ for 1H22in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)χ(3)]/αα values of the order of 10−11−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H22 were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[χ(3)χ(3)]/αα was almost three times higher in comparison with 1H22 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation
- Full Text:
- Date Issued: 2016
- Authors: Britton, Jonathan , Martynov, Alexander G , Oluwole, David O , Gorbunova, Yulia G , Tsivadze, Yulia G , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/239812 , vital:50769 , xlink:href="https://doi.org/10.1142/S1088424616501042"
- Description: This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxyphthalocyanine 1H22 and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H22 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)χ(3)]/αα, βeffβeff, and γγ for 1H22in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)χ(3)]/αα values of the order of 10−11−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H22 were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[χ(3)χ(3)]/αα was almost three times higher in comparison with 1H22 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation
- Full Text:
- Date Issued: 2016
Interaction of graphene quantum dots with 4-acetamido-2, 2, 6, 6-tetramethylpiperidine-oxyl free radicals
- Achadu, Ojodomo John, Nyokong, Tebello
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189031 , vital:44810 , xlink:href="https://doi.org/10.1007/s10895-015-1712-0"
- Description: We report on the interaction of graphene quantum dots (GQDs) with 4-acetamido-2,2,6,6-tetramethylpiperidineoxyl (4-acetamido-TEMPO) free radicals. The GQDs were N and S, N doped. The fluorescence quantum yields were higher for the doped GQDs compared to the undoped. The interaction is assessed by spectrofluorimetric, steady state/time resolved fluorescence and electron paramagnetic resonance (EPR) techniques. Fluorescence quenching was observed upon the addition of 4-acetamido-TEMPO to the GQDs. Photoinduced electron transfer (PET) mechanism was suggested as the plausible mechanism involved in the fluorescence quenching in which 4-acetamido-TEMPO acted as the electron acceptor.
- Full Text:
- Date Issued: 2016
- Authors: Achadu, Ojodomo John , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189031 , vital:44810 , xlink:href="https://doi.org/10.1007/s10895-015-1712-0"
- Description: We report on the interaction of graphene quantum dots (GQDs) with 4-acetamido-2,2,6,6-tetramethylpiperidineoxyl (4-acetamido-TEMPO) free radicals. The GQDs were N and S, N doped. The fluorescence quantum yields were higher for the doped GQDs compared to the undoped. The interaction is assessed by spectrofluorimetric, steady state/time resolved fluorescence and electron paramagnetic resonance (EPR) techniques. Fluorescence quenching was observed upon the addition of 4-acetamido-TEMPO to the GQDs. Photoinduced electron transfer (PET) mechanism was suggested as the plausible mechanism involved in the fluorescence quenching in which 4-acetamido-TEMPO acted as the electron acceptor.
- Full Text:
- Date Issued: 2016
MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine
- Mack, John, Mkhize, Scebi, Safonoya, Evgeniya A, Gorbunova, Yulia G, Tsivadze, Aslan Yu, Nyokong, Tebello
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
- Authors: Mack, John , Mkhize, Scebi , Safonoya, Evgeniya A , Gorbunova, Yulia G , Tsivadze, Aslan Yu , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240743 , vital:50867 , xlink:href="https://doi.org/10.1142/S1088424616500322"
- Description: An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A1𝒜1 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands.
- Full Text:
- Date Issued: 2016
Nonlinear optical behavior of alkyne terminated phthalocyanines in solution and when embedded in polysulfone as thin films: effects of aggregation
- Bankole, Owolabi M, Yilmaz, Yusuf, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Yilmaz, Yusuf , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189110 , vital:44817 , xlink:href="https://doi.org/10.1016/j.optmat.2015.11.041"
- Description: We report here for the first time, on the comparative studies of the photophysical and optical limiting behavior of our two novel phthalocyanines namely 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyanines 2, and 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyaninato zinc (II) (3) in solution and thin films. Nonlinear optical (NLO) properties of the samples in solution and contained in polysulfone (PSU) thin films were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. Effects of aggregation and disaggregation on the NLO performance of metal-free phthalocyanine are reported in detail. Our findings showed that the prepared Pcs show larger nonlinear absorption coefficient and lower limiting thresholds when embedded in polysulfone films compared to in solutions. The values of nonlinear susceptibility and hyperpolarizability recorded for 3-PSU in this work are respectively, ∼2.09 × 10−8 esu and ∼1.02 × 10−26 esu. These values are among the largest values reported for phthalocyanines and other macrocycles doped on polymer matrices.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Yilmaz, Yusuf , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189110 , vital:44817 , xlink:href="https://doi.org/10.1016/j.optmat.2015.11.041"
- Description: We report here for the first time, on the comparative studies of the photophysical and optical limiting behavior of our two novel phthalocyanines namely 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyanines 2, and 2(3), 9(10), 16(17), 23(24)-tetrakis-(4-(5-methylhex-1-yn-3-yloxy)) phthalocyaninato zinc (II) (3) in solution and thin films. Nonlinear optical (NLO) properties of the samples in solution and contained in polysulfone (PSU) thin films were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. Effects of aggregation and disaggregation on the NLO performance of metal-free phthalocyanine are reported in detail. Our findings showed that the prepared Pcs show larger nonlinear absorption coefficient and lower limiting thresholds when embedded in polysulfone films compared to in solutions. The values of nonlinear susceptibility and hyperpolarizability recorded for 3-PSU in this work are respectively, ∼2.09 × 10−8 esu and ∼1.02 × 10−26 esu. These values are among the largest values reported for phthalocyanines and other macrocycles doped on polymer matrices.
- Full Text:
- Date Issued: 2016
Nonlinear optical behavior of neodymium mono-and bi-nuclear phthalocyanines linked to zinc oxide nanoparticles and incorporated into poly acrylic acid
- Sekhosana, Kutloana E, Amuhaya, Edith, Nyokong, Tebello
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188766 , vital:44783 , xlink:href="https://doi.org/10.1016/j.poly.2015.12.045"
- Description: Syntheses of bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24))-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) and 2(3), 9(10), 16(17), 23(24)-(tetrapyridin-3-yloxy phthalocyaninato) neodymium (III) acetate (4) as well as their conjugates with ZnO nanoparticles (conjugates 6, 7 and 8) are presented. Thin films of conjugate 6 (where complex 3 is linked to ZnO nanoparticles via an amide bond) gave the best third-order susceptibility (5.89 × 10−8 esu), second-order hyperpolarizability (2.53 × 10−25 esu) and the lowest limiting threshold values (0.12 J cm−2). The nonlinear behavior is enhanced in solid state when compared to solution.
- Full Text:
- Date Issued: 2016
- Authors: Sekhosana, Kutloana E , Amuhaya, Edith , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188766 , vital:44783 , xlink:href="https://doi.org/10.1016/j.poly.2015.12.045"
- Description: Syntheses of bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24))-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) and 2(3), 9(10), 16(17), 23(24)-(tetrapyridin-3-yloxy phthalocyaninato) neodymium (III) acetate (4) as well as their conjugates with ZnO nanoparticles (conjugates 6, 7 and 8) are presented. Thin films of conjugate 6 (where complex 3 is linked to ZnO nanoparticles via an amide bond) gave the best third-order susceptibility (5.89 × 10−8 esu), second-order hyperpolarizability (2.53 × 10−25 esu) and the lowest limiting threshold values (0.12 J cm−2). The nonlinear behavior is enhanced in solid state when compared to solution.
- Full Text:
- Date Issued: 2016
Nonlinear optical response of a low symmetry phthalocyanine in the presence of gold nanoparticles when in solution or embedded in poly acrylic acid polymer thin films
- Bankole, Owolabi M, Nyokong, Tebello
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188719 , vital:44779 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.12.014"
- Description: In this article, we explored the photophysical and nonlinear optical (NLO) characterizations of low symmetry phthalocyanine (ZnPc-NH2) covalently linked to MPA-capped AuNPs (ZnPc-NH2-AuNPs) and poly acrylic acid (ZnPc-NH2-PAA). Nonlinear optical (NLO) properties of the samples were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. We observed enhanced photophysical and nonlinear optical behaviour for the ZnPc-NH2 in presence of AuNPs. By virtue of the magnitude of absorption coefficients and other NLO optical parameters estimated in this work, ZnPc-NH2-AuNPs was found to exhibit improved nonlinear optical response compared to the ZnPc-NH2 and ZnPc-NH2-PAA. Both ZnPc-NH2-AuNPs and ZnPc-NH2 doped in PAA possess strong nonlinear absorption coefficients and very low limiting thresholds than when measured in solution.
- Full Text:
- Date Issued: 2016
- Authors: Bankole, Owolabi M , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188719 , vital:44779 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.12.014"
- Description: In this article, we explored the photophysical and nonlinear optical (NLO) characterizations of low symmetry phthalocyanine (ZnPc-NH2) covalently linked to MPA-capped AuNPs (ZnPc-NH2-AuNPs) and poly acrylic acid (ZnPc-NH2-PAA). Nonlinear optical (NLO) properties of the samples were evaluated using Z-scan technique at 532 nm and 10 ns pulsed duration. We observed enhanced photophysical and nonlinear optical behaviour for the ZnPc-NH2 in presence of AuNPs. By virtue of the magnitude of absorption coefficients and other NLO optical parameters estimated in this work, ZnPc-NH2-AuNPs was found to exhibit improved nonlinear optical response compared to the ZnPc-NH2 and ZnPc-NH2-PAA. Both ZnPc-NH2-AuNPs and ZnPc-NH2 doped in PAA possess strong nonlinear absorption coefficients and very low limiting thresholds than when measured in solution.
- Full Text:
- Date Issued: 2016
Optical limiting response of multi-walled carbon nanotube-phthalocyanine nanocomposite in solution and when in poly (acrylic acid)
- Sekhosana, Kutloano E, Nyokong, Tebello
- Authors: Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188628 , vital:44770 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.03.067"
- Description: Bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24)-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) is linked to amino-functionalized multi-walled carbon nanotubes (MWCNT) to form 3-MWCNT. Z-scan technique was employed to experimentally determine the nonlinear absorption coefficient from the open-aperture data. The limiting threshold values as low as 0.045 J cm−2 were found in solution. The conjugate (3-MWCNT) gave better optical limiting behavior than complex 3 alone.
- Full Text:
- Date Issued: 2016
- Authors: Sekhosana, Kutloano E , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188628 , vital:44770 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.03.067"
- Description: Bis{23-(3,4-di-yloxybenzoic acid)-(2(3), 9(10), 16(17), 23(24)-(hexakis-pyridin-3-yloxy phthalocyaninato)} dineodymium (III) acetate (3) is linked to amino-functionalized multi-walled carbon nanotubes (MWCNT) to form 3-MWCNT. Z-scan technique was employed to experimentally determine the nonlinear absorption coefficient from the open-aperture data. The limiting threshold values as low as 0.045 J cm−2 were found in solution. The conjugate (3-MWCNT) gave better optical limiting behavior than complex 3 alone.
- Full Text:
- Date Issued: 2016
Optically active BODIPYs
- Lu, Hua, Mack, John, Nyokong, Tebello, Kobayashi, Nagao, Shen, Zhen
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
- Full Text:
- Date Issued: 2016
- Authors: Lu, Hua , Mack, John , Nyokong, Tebello , Kobayashi, Nagao , Shen, Zhen
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240421 , vital:50833 , xlink:href="https://doi.org/10.1016/j.ccr.2016.03.015"
- Description: This review highlights and summarizes various optically active BODIPY molecules and describes the analysis of their circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy, to provide a platform for the rational design of novel optically active BODIPY structures and the development of new chiroptical applications. Possible future research directions are also discussed.
- Full Text:
- Date Issued: 2016
Photophysical properties of tetraphenylporphyrinsubphthalocyanine conjugates
- Managa, Muthumuni, Mack, John, Remiro-Buenamañana, Sonia, Tshangana, Charmaine, Cammidge, Andrew N, Nyokong, Tebello
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Mack, John , Remiro-Buenamañana, Sonia , Tshangana, Charmaine , Cammidge, Andrew N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240766 , vital:50869 , xlink:href="https://doi.org/10.1142/S1088424615500959"
- Description: Novel tetraphenylporphyrin-subphthalocyanine conjugates have been prepared and characterized. An analysis of their optical spectroscopy and electronic structures using fluorescence emission and magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations, demonstrates that the two chromophores do not interact to any significant extent.
- Full Text:
- Date Issued: 2016
Photophysicochemical properties of nanoconjugates of zinc (II) 2 (3)-mono-2-(4-oxy) phenoxy) acetic acid phthalocyanine with cysteamine capped silver and silver–gold nanoparticles
- Oluwole, David O, Prinsloo, Earl, Nyokong, Tebello
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188552 , vital:44764 , xlink:href="https://doi.org/10.1016/j.poly.2016.09.034"
- Description: A novel asymmetrical zinc(II) 2(3)-mono-2-(4-oxy)phenoxy)acetic acid phthalocyanine (complex 1) was synthesized and subsequently linked to cysteamine capped silver (AgNPs) and silver–gold (AgAuNPs) nanoparticles (NPs) via amide bonds. The photophysicochemical properties and in vitro photodynamic therapy activity of complex 1 and its nanoconjugates were investigated. The nanoconjugates showed improved photophysical properties compared to complex 1 alone. The fluorescence, triplet and singlet quantum yields of complex 1 were found to be 20%, 48%, and 43% respectively. Complex 1 showed in vitro dark cytotoxicity, but the dark toxicity was reduced for the combination of complex 1 with AgAuNPs, this combination also gave the best photodynamic therapy activity when compared to complex 1 and its conjugate with AgNPs without AuNPs.
- Full Text:
- Date Issued: 2016
- Authors: Oluwole, David O , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188552 , vital:44764 , xlink:href="https://doi.org/10.1016/j.poly.2016.09.034"
- Description: A novel asymmetrical zinc(II) 2(3)-mono-2-(4-oxy)phenoxy)acetic acid phthalocyanine (complex 1) was synthesized and subsequently linked to cysteamine capped silver (AgNPs) and silver–gold (AgAuNPs) nanoparticles (NPs) via amide bonds. The photophysicochemical properties and in vitro photodynamic therapy activity of complex 1 and its nanoconjugates were investigated. The nanoconjugates showed improved photophysical properties compared to complex 1 alone. The fluorescence, triplet and singlet quantum yields of complex 1 were found to be 20%, 48%, and 43% respectively. Complex 1 showed in vitro dark cytotoxicity, but the dark toxicity was reduced for the combination of complex 1 with AgAuNPs, this combination also gave the best photodynamic therapy activity when compared to complex 1 and its conjugate with AgNPs without AuNPs.
- Full Text:
- Date Issued: 2016
Physicochemical and antimicrobial photodynamic chemotherapy of unsymmetrical indium phthalocyanines alone or in the presence of magnetic nanoparticles
- Osifeko, Olawale L, Uddin, Imran, Mashazi, Philani N, Nyokong, Tebello
- Authors: Osifeko, Olawale L , Uddin, Imran , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189121 , vital:44818 , xlink:href="https://doi.org/10.1039/C5NJ01922B"
- Description: An AB3 type photosensitiser, consisting of 4-pyridylsulfanyl units (denoted as B3) and one aminophenoxy (denoted as A) group (complex 3) was synthesized. Complex 3 was then quaternized to form complex 4. The aminophenoxy substituent of complex 3 was used for the formation of the amide linkage with the carboxylic functionalised magnetic nanoparticles. Complexes 3 and 4 and their conjugates with magnetic nanoparticles were then used for photodynamic antimicrobial chemotherapy on E. coli. The cationic photosensitiser 4 showed a high efficiency for photodynamic antimicrobial chemotherapy at a very low concentration compared to its conjugate on E. coli.
- Full Text:
- Date Issued: 2016
- Authors: Osifeko, Olawale L , Uddin, Imran , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189121 , vital:44818 , xlink:href="https://doi.org/10.1039/C5NJ01922B"
- Description: An AB3 type photosensitiser, consisting of 4-pyridylsulfanyl units (denoted as B3) and one aminophenoxy (denoted as A) group (complex 3) was synthesized. Complex 3 was then quaternized to form complex 4. The aminophenoxy substituent of complex 3 was used for the formation of the amide linkage with the carboxylic functionalised magnetic nanoparticles. Complexes 3 and 4 and their conjugates with magnetic nanoparticles were then used for photodynamic antimicrobial chemotherapy on E. coli. The cationic photosensitiser 4 showed a high efficiency for photodynamic antimicrobial chemotherapy at a very low concentration compared to its conjugate on E. coli.
- Full Text:
- Date Issued: 2016
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
Synthesis and dark toxicity of 5-(4-carboxyphenyl)-10, 15, 20-tris (phenyl)-porphyrinato chlorido gallium (III) when conjugated to δ-aminolevulinic acid
- Managa, Muthumuni, Mkhize, Scebi, Britton, Jonathan, Prinsloo, Earl, Nyokong, Tebello
- Authors: Managa, Muthumuni , Mkhize, Scebi , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240014 , vital:50789 , xlink:href="https://doi.org/10.1080/00958972.2016.1223292"
- Description: 5-(4-Carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato chlorido gallium(III) (2) was synthesized and then linked to ethyl ester δ-aminolevulinic acid to form 3. There was no shift in Soret band following conjugation. The fluorescence and singlet oxygen generating behavior of the porphyrins were also investigated. The highest singlet oxygen quantum yield (ΦΔ) obtained was that of 3. Complexes 2 and 3 as well as metal free 5-(4-carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato showed no dark toxicity on MCF-7 breast cancer cells.
- Full Text:
- Date Issued: 2016
- Authors: Managa, Muthumuni , Mkhize, Scebi , Britton, Jonathan , Prinsloo, Earl , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240014 , vital:50789 , xlink:href="https://doi.org/10.1080/00958972.2016.1223292"
- Description: 5-(4-Carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato chlorido gallium(III) (2) was synthesized and then linked to ethyl ester δ-aminolevulinic acid to form 3. There was no shift in Soret band following conjugation. The fluorescence and singlet oxygen generating behavior of the porphyrins were also investigated. The highest singlet oxygen quantum yield (ΦΔ) obtained was that of 3. Complexes 2 and 3 as well as metal free 5-(4-carboxyphenyl)-10,15,20-tris(phenyl)-porphyrinato showed no dark toxicity on MCF-7 breast cancer cells.
- Full Text:
- Date Issued: 2016
Synthesis and optical limiting properties of new lanthanide bis-and tris-phthalocyanines
- Sekhosana, Kutloana Edward, Manyeruke, Meloddy Hlatini, Nyokong, Tebello
- Authors: Sekhosana, Kutloana Edward , Manyeruke, Meloddy Hlatini , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240063 , vital:50795 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.05.068"
- Description: This manuscript reports on syntheses of new multi-decker phthalocyanines, namely: bis-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} cerium(III) (2), tris-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} dicerium(III) (4) and bis-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} gadolinium(III) (5). Complex 4 which is a tris phthalocyanine showed better nonlinear optical behavior in solution than 2 which is a bis phthalocyanine, both containing the same central metal, Ce. All the three molecules possess good optical limiting properties judged by the limiting threshold values which ranged from 0.04 to 0.09 J cm−2 with complex 5 embedded in thin films, showing the lowest value of 0.04 J cm−2. Furthermore, nonlinear optical processes responsible for reverse saturable absorption data are investigated.
- Full Text:
- Date Issued: 2016
- Authors: Sekhosana, Kutloana Edward , Manyeruke, Meloddy Hlatini , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/240063 , vital:50795 , xlink:href="https://doi.org/10.1016/j.molstruc.2016.05.068"
- Description: This manuscript reports on syntheses of new multi-decker phthalocyanines, namely: bis-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} cerium(III) (2), tris-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} dicerium(III) (4) and bis-{2,3,9,10,16,10,16,17,23,24-octa(4-tertbutylphenoxy) phthalocyaninato} gadolinium(III) (5). Complex 4 which is a tris phthalocyanine showed better nonlinear optical behavior in solution than 2 which is a bis phthalocyanine, both containing the same central metal, Ce. All the three molecules possess good optical limiting properties judged by the limiting threshold values which ranged from 0.04 to 0.09 J cm−2 with complex 5 embedded in thin films, showing the lowest value of 0.04 J cm−2. Furthermore, nonlinear optical processes responsible for reverse saturable absorption data are investigated.
- Full Text:
- Date Issued: 2016
Synthesis and photophysicochemical properties of BODIPY dye functionalized gold nanorods for use in antimicrobial photodynamic therapy
- Kubheka, Gugu, Uddin, Imran, Amuhaya, Edith, Mack, John, Nyokong, Tebello
- Authors: Kubheka, Gugu , Uddin, Imran , Amuhaya, Edith , 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 , 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 physicochemical properties of zinc and indium phthalocyanines conjugated to quantum dots, gold and magnetic nanoparticles
- Osifeko, Olawale, Nyokong, Tebello
- Authors: Osifeko, Olawale , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188639 , vital:44771 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.04.015"
- Description: This work reports on the conjugation of semiconductors quantum dots (QDs), gold (AuNPs) or Fe3O4 magnetic (MNPs) nanoparticles to 4-(4,6-diaminopyrimidin-2-ylthio) substituted indium or zinc phthalocyanines (Pcs). The QDs and MNPs were linked to the Pcs via an amide bond and by chemisorption unto AuNP surface. There is a general decrease in fluorescence quantum yields of the Pcs in the presence of all the nanoparticles. There is an increase triplet quantum yields for Pcs in the presence of AuNPs and QDs, but not in the presence of MNPs. AuNPs conjugates irrespective of the central atoms have the highest singlet oxygen quantum yield and are more photo-stable than all the other conjugates. MPcs are less photostable in the presence of MNPs.
- Full Text:
- Date Issued: 2016
- Authors: Osifeko, Olawale , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188639 , vital:44771 , xlink:href="https://doi.org/10.1016/j.dyepig.2016.04.015"
- Description: This work reports on the conjugation of semiconductors quantum dots (QDs), gold (AuNPs) or Fe3O4 magnetic (MNPs) nanoparticles to 4-(4,6-diaminopyrimidin-2-ylthio) substituted indium or zinc phthalocyanines (Pcs). The QDs and MNPs were linked to the Pcs via an amide bond and by chemisorption unto AuNP surface. There is a general decrease in fluorescence quantum yields of the Pcs in the presence of all the nanoparticles. There is an increase triplet quantum yields for Pcs in the presence of AuNPs and QDs, but not in the presence of MNPs. AuNPs conjugates irrespective of the central atoms have the highest singlet oxygen quantum yield and are more photo-stable than all the other conjugates. MPcs are less photostable in the presence of MNPs.
- Full Text:
- Date Issued: 2016
Synthesis and singlet oxygen production by a phthalocyanine when embedded in asymmetric polymer membranes
- Mafukidze, Donovan M, Mashazi, Philani N, Nyokong, Tebello
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
- Full Text:
- Date Issued: 2016
- Authors: Mafukidze, Donovan M , Mashazi, Philani N , Nyokong, Tebello
- Date: 2016
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/188563 , vital:44765 , xlink:href="https://doi.org/10.1016/j.polymer.2016.10.032"
- Description: 2(3), 9(10), 16(17), 23(24)-Tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (ClInTAPPc, 3) was first conjugated to two different polymers: polystyrene (PS) and polyacrylonitrile (PAN) to form 3-PS and 3-PAN. The conjugates were cast into the corresponding polymers to form membranes represented as 3-PS-membrane and 3-PAN-membrane, respectively. The prepared membranes were characterized using various techniques including scanning electron microscopy and solid state UV/Vis spectroscopy. Singlet oxygen quantum yields were higher for the 3-PS-membrane at 0.51 compared to 3-PAN-membrane at 0.35. The larger singlet oxygen also applies to 3-PS (0.63) compared to 3-PAN (0.38) when in solution.
- Full Text:
- Date Issued: 2016
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