Nonlinear optical properties of Sn(IV) phthalocyanines: experimental and theoretical approach
- Authors: Louzada, Marcel Severiano
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/57852 , vital:26996
- Description: This work presents the nonlinear properties of six Sn(IV) Phthalocyanines. Three of the phthalocyanines are linked by an alkylthiol substituent and the rest are linked with a phenoxy substituent. For all six compounds non-linear optic analysis was carried out in four solvents: chloroform, toluene, dichloromethane, and tetrahydrofuran, and their differences were recorded. Calculation of the linear, singlet excited, triplet excited and two photon absorption cross-sections were also carried out and the results compared. To form a comparison the first order hyperpolarizabilities, DFT calculations were also performed and the results compared to see if the behaviour between the two properties can be predicted using DFT.
- Full Text:
- Date Issued: 2017
- Authors: Louzada, Marcel Severiano
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/57852 , vital:26996
- Description: This work presents the nonlinear properties of six Sn(IV) Phthalocyanines. Three of the phthalocyanines are linked by an alkylthiol substituent and the rest are linked with a phenoxy substituent. For all six compounds non-linear optic analysis was carried out in four solvents: chloroform, toluene, dichloromethane, and tetrahydrofuran, and their differences were recorded. Calculation of the linear, singlet excited, triplet excited and two photon absorption cross-sections were also carried out and the results compared. To form a comparison the first order hyperpolarizabilities, DFT calculations were also performed and the results compared to see if the behaviour between the two properties can be predicted using DFT.
- Full Text:
- Date Issued: 2017
Nonlinear optical responses of phthalocyanines in the presence of nanomaterials or when embedded in polymeric materials
- Authors: Bankole, Owolabi Mutolib
- Date: 2017
- Subjects: Phthalocyanines , Phthalocyanines -- Optical properties , Alkynes , Triazoles , Nonlinear optics , Photochemistry , Complex compounds , Amines , Mercaptopyridine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/45794 , vital:25548
- Description: This work describes the synthesis, photophysical and nonlinear optical characterizations of alkynyl Pcs (1, 2, 3, 8 and 9), 1,2,3-triazole ZnPc (4), mercaptopyridine Pcs (5, 6 and 7) and amino Pcs (10 and 11). Complexes 1, 2, 4, 7, 8, 9 and 11 were newly synthesized and characterized using techniques including 1H-NMR, MALDI-TOF, UV-visible spectrophotometry, FTIR and elemental analysis. The results of the characterizations were in good agreement with their molecular structures, and confirmed the purity of the new molecules. Complex 10 was covalently linked to pristine graphene (GQDs), nitrogen- doped (NGQDs), and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots; gold nanoparticles (AuNPs); poly(acrylic acid) (PAA); Fe3O4@Ag core-shell and Fe3O4- Ag hybrid nanoparticles via covalent bonding. Complex 11 was linked to Agx Auy alloy nanoparticles via NH2-Au and/or Au-S bonding, 2 and 3 were linked to gold nanoparticles (AuNPs) via clicked reactions. Evidence of successful conjugation of 2, 3, 10 and 11 to nanomaterials was revealed within the UV-vis, EDS, TEM, XRD and XPS spectra. Optical limiting (OL) responses of the samples were evaluated using open aperture Z-scan technique at 532 nm and 10 ns radiation in solution or when embedded in polymer mixtures. The analyses of the Z-scan data for the studied samples did fit to a two-photon absorption mechanism (2PA), but the Pcs and Pc-nanomaterial or polymer composites also possess the multi-photon absorption mechanisms aided by the triplet-triplet population to have reverse saturable absorption (RSA) occur. Phthalocyanines doped in polymer matrices showed larger nonlinear absorption coefficients (ßeff), third-order susceptibility (Im [x(3)]) and second-order hyperpolarizability (y), with an accompanying low intensity threshold (Ium) than in solution. Aggregation in DMSO negatively affected NLO behaviour of Pcs (8 as a case study) at low laser power, and improved at relatively higher laser power. Heavy atom-substituted Pcs (6) enhanced NLO and OL properties than lighter atoms such as 5 and 7. Direct relationship between enhanced photophysical properties and nonlinear effects favoured by excited triplet absorption of the 2, 3, 10 and 11 in presence of nanomaterials was established. Major factor responsible for the enhanced nonlinearities of 10 in the presence of NGQDs and SNGQDs were fully described and attributed to the surface defects caused by the presence of heteroatoms such as nitrogen and sulfur. The studies showed that phthalocyanines-nanomaterial composites were useful in applications such as optical switching, pulse compressor and laser pulse narrowing.
- Full Text:
- Date Issued: 2017
- Authors: Bankole, Owolabi Mutolib
- Date: 2017
- Subjects: Phthalocyanines , Phthalocyanines -- Optical properties , Alkynes , Triazoles , Nonlinear optics , Photochemistry , Complex compounds , Amines , Mercaptopyridine
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10962/45794 , vital:25548
- Description: This work describes the synthesis, photophysical and nonlinear optical characterizations of alkynyl Pcs (1, 2, 3, 8 and 9), 1,2,3-triazole ZnPc (4), mercaptopyridine Pcs (5, 6 and 7) and amino Pcs (10 and 11). Complexes 1, 2, 4, 7, 8, 9 and 11 were newly synthesized and characterized using techniques including 1H-NMR, MALDI-TOF, UV-visible spectrophotometry, FTIR and elemental analysis. The results of the characterizations were in good agreement with their molecular structures, and confirmed the purity of the new molecules. Complex 10 was covalently linked to pristine graphene (GQDs), nitrogen- doped (NGQDs), and sulfur-nitrogen co-doped (SNGQDs) graphene quantum dots; gold nanoparticles (AuNPs); poly(acrylic acid) (PAA); Fe3O4@Ag core-shell and Fe3O4- Ag hybrid nanoparticles via covalent bonding. Complex 11 was linked to Agx Auy alloy nanoparticles via NH2-Au and/or Au-S bonding, 2 and 3 were linked to gold nanoparticles (AuNPs) via clicked reactions. Evidence of successful conjugation of 2, 3, 10 and 11 to nanomaterials was revealed within the UV-vis, EDS, TEM, XRD and XPS spectra. Optical limiting (OL) responses of the samples were evaluated using open aperture Z-scan technique at 532 nm and 10 ns radiation in solution or when embedded in polymer mixtures. The analyses of the Z-scan data for the studied samples did fit to a two-photon absorption mechanism (2PA), but the Pcs and Pc-nanomaterial or polymer composites also possess the multi-photon absorption mechanisms aided by the triplet-triplet population to have reverse saturable absorption (RSA) occur. Phthalocyanines doped in polymer matrices showed larger nonlinear absorption coefficients (ßeff), third-order susceptibility (Im [x(3)]) and second-order hyperpolarizability (y), with an accompanying low intensity threshold (Ium) than in solution. Aggregation in DMSO negatively affected NLO behaviour of Pcs (8 as a case study) at low laser power, and improved at relatively higher laser power. Heavy atom-substituted Pcs (6) enhanced NLO and OL properties than lighter atoms such as 5 and 7. Direct relationship between enhanced photophysical properties and nonlinear effects favoured by excited triplet absorption of the 2, 3, 10 and 11 in presence of nanomaterials was established. Major factor responsible for the enhanced nonlinearities of 10 in the presence of NGQDs and SNGQDs were fully described and attributed to the surface defects caused by the presence of heteroatoms such as nitrogen and sulfur. The studies showed that phthalocyanines-nanomaterial composites were useful in applications such as optical switching, pulse compressor and laser pulse narrowing.
- Full Text:
- Date Issued: 2017
Tetra 4-(propargyloxy)phenoxy phthalocyanines: synthesis, spectroscopic, nonlinear optical and electrocatalytic properties
- Authors: Mwanza, Daniel
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics , Electrocatalysis , Spectrum analysis , Thermogravimetry , Phthalocyanines Spectra
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65144 , vital:28695
- Description: This study presents the synthesis, spectroscopic, photophysical and theoretical characterisation of metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (MnTPrOPhOPc) tetra 4-(4-propargyloxy) phenoxy phthalocyanines. Thermal analysis using thermogravimetric analysis (TGA) confirmed the excellent thermal stability of synthesized tetra 4-(4- propargyloxy) phenoxy phthalocyanines. The metal complexes, CoTPrOPhOPc and MnTPrOPhOPc, exhibited better thermal stability when compared to H2TPrOPhOPc. The residual percentage weight remaining was approximately 70% for CoTPrOPhOPc and MnTPrOPhOPc and 45% for H2TPrOPhOPc after 600°C, clearly confirming the stability of the metal complexes. The MTPrOPhOPcs (where M = H2, Co and Mn) complexes exhibited excellent nonlinear optical properties with strong reverse saturable absorption (RSA), especially when 560 nm excitation laser was used. Their nonlinear optical properties followed this trend: H2TPrOPhOPc > CoTPrOPhOPc > MnTPrOPhOPc. According to the trend observed, the H2TPrOPhOPc was an excellent nonlinear optical limiter when compared to the CoTPrOPhOPc and MnTPrOPhOPc. All the investigated complexes exhibited optical limiting properties comparable to the phthalocyanine complexes reported in the literature. The MTPrOPhOPc complexes were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. For the electrocatalytic studies, the synthesized complexes were immobilized onto gold electrode surfaces pre-functionalized with phenylazide (Au-PAz) monolayer. Copper (I) catalyzed alkynyl-azide cycloaddition reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs modified gold surfaces (Au-PAz-MTPrOPhOPc) exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and surface characterisation of the functionalised gold electrode surfaces confirmed the presence of the MTPrOPhOPcs and their electroanalysis was excellent towards electrocatalytic reduction of H2O2, with the limit of detection (LoD) and limit of quantification (LoQ) in the ^M range. The electrocatalytic reduction peaks for H2O2 were observed at -0.37 V for Au-PAz-MnTPrOPhOPc and -0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-MnTPrOPhOPc and Au- PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution. , Thesis (MSc) -- Faculty of Science, Chemistry, 2017
- Full Text:
- Date Issued: 2017
- Authors: Mwanza, Daniel
- Date: 2017
- Subjects: Phthalocyanines , Nonlinear optics , Electrocatalysis , Spectrum analysis , Thermogravimetry , Phthalocyanines Spectra
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10962/65144 , vital:28695
- Description: This study presents the synthesis, spectroscopic, photophysical and theoretical characterisation of metal-free (H2TPrOPhOPc), cobalt (CoTPrOPhOPc) and manganese (MnTPrOPhOPc) tetra 4-(4-propargyloxy) phenoxy phthalocyanines. Thermal analysis using thermogravimetric analysis (TGA) confirmed the excellent thermal stability of synthesized tetra 4-(4- propargyloxy) phenoxy phthalocyanines. The metal complexes, CoTPrOPhOPc and MnTPrOPhOPc, exhibited better thermal stability when compared to H2TPrOPhOPc. The residual percentage weight remaining was approximately 70% for CoTPrOPhOPc and MnTPrOPhOPc and 45% for H2TPrOPhOPc after 600°C, clearly confirming the stability of the metal complexes. The MTPrOPhOPcs (where M = H2, Co and Mn) complexes exhibited excellent nonlinear optical properties with strong reverse saturable absorption (RSA), especially when 560 nm excitation laser was used. Their nonlinear optical properties followed this trend: H2TPrOPhOPc > CoTPrOPhOPc > MnTPrOPhOPc. According to the trend observed, the H2TPrOPhOPc was an excellent nonlinear optical limiter when compared to the CoTPrOPhOPc and MnTPrOPhOPc. All the investigated complexes exhibited optical limiting properties comparable to the phthalocyanine complexes reported in the literature. The MTPrOPhOPc complexes were further studied for their electrocatalytic and electroanalytical properties towards the detection of hydrogen peroxide. For the electrocatalytic studies, the synthesized complexes were immobilized onto gold electrode surfaces pre-functionalized with phenylazide (Au-PAz) monolayer. Copper (I) catalyzed alkynyl-azide cycloaddition reaction was used to covalently immobilize the MTPrOPhOPcs onto the gold electrode surfaces to form Au-PAz-MTPrOPhOPc. The MTPrOPhOPcs modified gold surfaces (Au-PAz-MTPrOPhOPc) exhibited good reproducibility and stability in various electrolyte conditions. Electrochemical and surface characterisation of the functionalised gold electrode surfaces confirmed the presence of the MTPrOPhOPcs and their electroanalysis was excellent towards electrocatalytic reduction of H2O2, with the limit of detection (LoD) and limit of quantification (LoQ) in the ^M range. The electrocatalytic reduction peaks for H2O2 were observed at -0.37 V for Au-PAz-MnTPrOPhOPc and -0.31 V for Au-PAz-CoTPrOPhOPc when Ag|AgCl pseudo-reference electrode was used. The Au-PAz-MnTPrOPhOPc and Au- PAz-CoTPrOPhOPc gold electrode surfaces showed good sensitivity and reproducibility towards the electrocatalytic reduction of hydrogen peroxide in pH 7.4 phosphate buffer solution. , Thesis (MSc) -- Faculty of Science, Chemistry, 2017
- Full Text:
- Date Issued: 2017
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