Optical limiting properties of 3, 5-dipyrenylvinyleneBODIPY dyes at 532 nm
- Authors: Kubheka, Gugu , Sanusi, Kayode , Mack, John , Nyokong, Tebello
- Date: 2018
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/237938 , vital:50567 , xlink:href="https://doi.org/10.1016/j.saa.2017.10.021"
- Description: The optical limiting (OL) properties of 3,5-dipyrenylvinyleneBODIPY dyes that contain both electron withdrawing and donating moieties have been investigated by using the z-scan technique at 532 nm in the nanosecond pulse range. The extension of the π-conjugation at the 3,5-positions with pyrenylvinylene groups results in a ca. 200 nm red shift of the main BODIPY spectral band to ca. 700 nm, so there is relatively weak absorbance at 532 nm under ambient light conditions. Reverse saturable absorbance (RSA) profiles are observed in response to incident pulsed laser light that is consistent with a two photon absorption-assisted excited state absorption (ESA) mechanism in CH2Cl2 solution and when the dyes are embedded in poly(bisphenol carbonate A) (PBC) polymer thin films. This demonstrates that 3,5-divinyleneBODIPY dyes are potentially suitable for use in OL applications, since limiting threshold fluence (Ilim) values of below 0.95 J cm−2 are observed when thin films are prepared.
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Enhanced optical limiting behaviour of indium phthalocyanine derivatives when in solution or embedded in poly (acrylic acid) or poly (methyl methacrylate) polymers
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2015
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189445 , vital:44847 , xlink:href="https://doi.org/10.1016/j.jphotochem.2015.02.003"
- Description: The optical limiting performance of indium phthalocyanine-based polymer thin-films with large nonlinear absorption coefficients (βeff) and low limiting threshold intensity (Ilim) are described. The absorption cross-sections and the population dynamics of the excited states are also reported. The excited state absorption cross-sections (σexc) are shown to depend on the transition moment between the T1 and T2 states. βeff values have been shown to be related to the population density of the molecules in the T1 state. The improved optical limiting performance recorded for the investigated phthalocyanine complexes in the presence of polymer matrices has been attributed to the aggregation effects of the complexes in the polymer thin-films. The optical properties of the indium phthalocyanine moieties were found to possess robust sensitivity to a change of the polymer materials.
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Effects of pyrene on the photophysical and two-photon absorption-based nonlinear optical properties of indium (III) phthalocyanines
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189957 , vital:44951 , xlink:href="https://doi.org/10.1080/00958972.2014.959509"
- Description: Photophysical and two-photon-dependent nonlinear absorption properties of two chloroindium(III) phthalocyanines bearing pyrene units have been investigated. The tetra- (3) and the tri- (4) pyrene-substituted phthalocyanines exhibit strong triplet absorption with high triplet yields ( ) of 0.79 and 0.83, respectively. The measured nonlinear optical data, such as the two photon absorption cross-sections, the third- and second-order nonlinearities were found to be comparable with those of literature, thus, making the compounds promising candidates for a broad range of nonlinear optical applications.
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Enhanced Optical Limiting Behavior of an Indium Phthalocyanine–Single-Walled Carbon Nanotube Composite
- Authors: Sanusi, Kayode , Amuhaya, Edith K , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193871 , vital:45401 , xlink:href="https://doi.org/10.1021/jp501469e "
- Description: The nonlinear optical behavior of 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy) phthalocyaninato indium (III) chloride (2) and its carbon nanotube composite in dimethylsulfoxide (DMSO) and dimethylformamide (DMF) solutions is described. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. A large nonlinear absorption that increased on covalent linking with single-walled carbon nanotubes (SWCNTs) was observed for the compound in DMSO. The nanosecond nonlinear absorption and the optical limiting behavior of this complex are shown to be dominated by a strong excited state absorption from a two-photon pumped state. The optical limiter using the new nanocomposite material (SWCNT-2) in the appropriate solvent showed a much lower threshold for optical limiting together with a much lower transmission at high fluences than previously reported nanocomposite limiters. The optical properties of the phthalocyanine and its conjugate were found to show high sensitivity toward the change of solvent matrix.
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Enhanced optical limiting performance in phthalocyanine-quantum dot nanocomposites by free-carrier absorption mechanism
- Authors: Sanusi, Kayode , Khene, Samson M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/193904 , vital:45404 , xlink:href="https://doi.org/10.1016/j.optmat.2014.07.024"
- Description: Enhanced nonlinear optical properties (in dimethyl sulphoxide) is observed for 2(3),9(10),16(17),23(24)-tetrakis-(4-aminophenoxy)phthalocyaninato indium(III) chloride (InPc) when covalently linked to CdSe/ZnS or CdSe quantum dots (QDs). The experimental nonlinear optical parameters were obtained from Z-Scan measurements. Contributions from two-photon absorption (2PA) due to the InPc, and free-carrier absorption (FCA) by QDS have been identified as the main factors responsible for the enhanced optical limiting. The effective nonlinear absorption coefficient for InPc-CdSe/ZnS was found to be 700.0 cm/GW. The FCA cross-sections for InPc-CdSe/ZnS and InPc-CdSe composites were found to be 1.52 × 10−19 and 6.00 × 10−20 cm2 respectively. A much lower limiting threshold of 92 mJ cm−2 was observed for InPc-CdSe/ZnS nanocomposite, hence, making it suitable for use as optical limiting material. Density Functional Theory (DFT) calculations on similar phthalocyanine-quantum dots system was modeled in order to explain the enhancement in the observed nonlinear optical properties of the Pc in the presence of the QDs. The experimentally determined nonlinear optical properties are well within the range of the DFT calculated properties.
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Indium phthalocyanine–CdSe/ZnS quantum dots nanocomposites showing size dependent and near ideal optical limiting behaviour
- Authors: Sanusi, Kayode , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/189921 , vital:44947 , xlink:href="https://doi.org/10.1016/j.optmat.2014.09.021"
- Description: Indium phthalocyanine–CdSe/ZnS quantum dots (QDs) nanocomposites (InPc–CdSe/ZnS) of three sizes (5.57, 8.12 and 8.75 nm) were synthesized according to known procedures. The particle size of the CdSe/ZnS QDs alone are 3.95, 6.02, and 6.66 nm, and are denoted as QD1, QD2 and QD3 respectively. The nonlinear absorption (NLA) properties of the nanoconjugates (InPc–CdSe/ZnS) were investigated with nanosecond laser radiation at 532 nm wavelength. Enhanced NLA properties compared to the InPc alone were observed in the conjugates. The NLA was found to increase with the size of the CdSe/ZnS particles attached to the phthalocyanine. The observed increase was due to the availability of more free-carrier ions in the larger QDs, thus giving rise to the enhanced free-carrier absorption. The measured free-carrier absorption cross-sections (σFCA) are 1.10, 1.65 and 1.95 (×10−19 cm2) for InPc-QD1, InPc-QD2 and InPc-QD3 respectively. The nanoconjugates (InPc–CdSe/ZnS) showed a much lower threshold for optical limiting together with a much lower transmission at high fluences, than the previously reported nanocomposite limiters.
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Optical nonlinearities in non-peripherally substituted pyridyloxy phthalocyanines
- Authors: Sanusi, Kayode , Antunes, Edith M , Nyokong, Tebello
- Date: 2014
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/241618 , vital:50955 , xlink:href="https://doi.org/10.1039/C3DT52462K"
- Description: The optical nonlinearities of six non-peripherally-substituted pyridyloxy phthalocyanines have been studied at 532 nm using a nanosecond Z-scan technique in a dimethyl sulphoxide solution. Ring-strain effects and the absence of a metal center were found to greatly reduce the inherent high nonlinearities expected of some of these phthalocyanine complexes. Of the six molecules investigated, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyaninato lead(II) 3, 1(4),8(11),15(18),22(25)-tetrakis-(2-pyridyloxy)phthalocyanine 5, and 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyanine 6 were found to exhibit negligible nonlinear optical behavior, due to either the absence of asymmetry or central metal and/or the presence of a ring-strain effect. A two-photon absorption process was found to be the major contributor to the observed reverse saturable absorption (RSA) in 1(4),8(11),15(18),22(25)-tetrakis-(4-pyridyloxy)phthalocyaninato lead(II) 4, 1(4)-mono-(2-pyridyloxy)phthalocyaninato lead(II) 7, and 1(4)-mono-(4-pyridyloxy)phthalocyaninato lead(II) 8, with large two-photon absorption cross-section, high hyperpolarizability and high third-order susceptibility values in the range of 4.53 × 10−43–5.33 × 10−42 cm4 s per photon, 1.61 × 10−28–1.89 × 10−27 esu and 9.73 × 10−12–7.05 × 10−11 esu respectively.
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