Synthesis, spectroscopic and nonlinear optical properties of asymmetric A3B type phthalocyanine complexes
- Authors: Mugeza, Rhulani Donney
- Date: 2021
- Subjects: Spectrum analysis , Mass spectrometry , Phthalocyanines
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/171667 , vital:42108
- Description: This work reports on the synthesis of symmetrical and asymmetrical A 3 B type metal free, cobalt and zinc Phthalocyanines (Pc) .A wide range of spectroscopic techniques such as Uv - visible absorption (UV), magnetic circular dichroism (MCD), mass spectrometry, elemental analysis, IR spectroscopy and time correlated single photo n counting spectroscopy (TCSPC) have been used to study the spectroscopic properties of the phthalocyanine complexes. The Z - scan technique was used to comparatively investigate the nonlinear absorption coefficient ( 휷 ) and the nonlinear refraction index ( 풏 ퟐ ) of the synthesized complexes. The following trend was obtained for the synthesized Pc’s in terms of the 휷 values 7.25 × 10 − 10 ( 4b ) > 3.76 × 10 − 10 ( 4a ) > 3.52 × 10 − 10 ( 4c ) > 2.29 × 10 − 10 ( 3c ) > 1.68 × 10 − 10 ( 3a ) > 1.65 × 10 − 10 ( 3b ) mW - 1 . The 휷 values trend of synthesized Pc complexes show that the asymmetrical A 3 B type metal free, cobalt and zinc Pc complexes ( 4a , 4b and 4c ) have larger 휷 values as compared to the octa - substituted symmetrical metal free, cobalt and zinc Pc complexes ( 3a , 3b and 3c ) which is attributed to the low symmetry of the Pc complexes. The five - level model rate equations were used to determine the two photon absorption, excited state absorption and ground state absorption cross sections of the synthesized complexes. The z inc A 3 B type asymmetrical Pc complexes gave the largest two photon absorption and 휎 푒 / 휎 푔 ratio values. This Pc complex could be used in future work to enhance the nonlinear response further by introducing nanomaterials and converting the Pc complex to a binuclear Pc. This work also reports on the density functional theory (DFT) calculations o f dipolar/octupolar contributions in order to study the first order hyperpolarizability of the synthesized Pc complexes.
- Full Text:
- Date Issued: 2021
- Authors: Mugeza, Rhulani Donney
- Date: 2021
- Subjects: Spectrum analysis , Mass spectrometry , Phthalocyanines
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/171667 , vital:42108
- Description: This work reports on the synthesis of symmetrical and asymmetrical A 3 B type metal free, cobalt and zinc Phthalocyanines (Pc) .A wide range of spectroscopic techniques such as Uv - visible absorption (UV), magnetic circular dichroism (MCD), mass spectrometry, elemental analysis, IR spectroscopy and time correlated single photo n counting spectroscopy (TCSPC) have been used to study the spectroscopic properties of the phthalocyanine complexes. The Z - scan technique was used to comparatively investigate the nonlinear absorption coefficient ( 휷 ) and the nonlinear refraction index ( 풏 ퟐ ) of the synthesized complexes. The following trend was obtained for the synthesized Pc’s in terms of the 휷 values 7.25 × 10 − 10 ( 4b ) > 3.76 × 10 − 10 ( 4a ) > 3.52 × 10 − 10 ( 4c ) > 2.29 × 10 − 10 ( 3c ) > 1.68 × 10 − 10 ( 3a ) > 1.65 × 10 − 10 ( 3b ) mW - 1 . The 휷 values trend of synthesized Pc complexes show that the asymmetrical A 3 B type metal free, cobalt and zinc Pc complexes ( 4a , 4b and 4c ) have larger 휷 values as compared to the octa - substituted symmetrical metal free, cobalt and zinc Pc complexes ( 3a , 3b and 3c ) which is attributed to the low symmetry of the Pc complexes. The five - level model rate equations were used to determine the two photon absorption, excited state absorption and ground state absorption cross sections of the synthesized complexes. The z inc A 3 B type asymmetrical Pc complexes gave the largest two photon absorption and 휎 푒 / 휎 푔 ratio values. This Pc complex could be used in future work to enhance the nonlinear response further by introducing nanomaterials and converting the Pc complex to a binuclear Pc. This work also reports on the density functional theory (DFT) calculations o f dipolar/octupolar contributions in order to study the first order hyperpolarizability of the synthesized Pc complexes.
- Full Text:
- Date Issued: 2021
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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