Njemuwa Nwaji

Synthesis, photophysical and nonlinear optical properties of a series of ball-type phthalocyanines in solution and thin films

In this study, we report on the enhanced nonlinear optical properties of novel tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato zinc(II)) (4), tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato gallium chloride) (5) and tetrakis-4-(hexadecane-1,2-dioxyl)-bis(phthalocyaninato indium chloride) (6) both in solution and when embedded in polymer thin films. Complexes 5 and 6 bearing heavy atoms showed enhanced triplet quantum yield and nonlinear optical response. The nonlinear third-order susceptibility and second-order hyperpolarizability values are also reported. Time dependent density functional theory (TD-DFT) calculations were performed in order to explain the origin of the observed UV-vis and magnetic circular dichroism (MCD) spectra of the complexes.

Photophysical and nonlinear optical study of benzothiazole substituted phthalocyanines in solution and thin films

In this study, the photophysical, nonlinear absorption and nonlinear optical limiting properties of zinc and gallium phthalocyanine complexes: tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (3), tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato] gallium(III) chloride (4), tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] zinc(II) (5), tetrakis[(benzo[d]thiazol-2-ylthio)phthalocyaninato] gallium(III) chloride (6), were investigated both in solution and when embedded in polystyrene thin films using 532 nm laser excitation at 10 ns pulses. It was also observed that complexes that have higher triplet state absorption also possessed enhanced nonlinear and optical limiting behavior. Superior optical performance was observed when the complexes were embedded in thin films compared to when they are in solution. Complex 6 in thin films gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 4.61 × 10-7 esu and 3.44 × 10-26 esu, respectively, with a low Ilim value of 0.06 J.cm-2

Photophysical and optical limiting properties at 532 nm of BODIPY dyes with p-benzyloxystyryl groups at the 3,5-positions

The synthesis and characterization of a series of 3,5-di-p-benzyloxystyrylBODIPY dyes with different substituents at the meso-aryl position is reported. The photophysical and nonlinear optical properties are described. BODIPYs of this type are found to be suitable for optical limiting at 532 nm on the nanosecond timescale. An enhancement of the population of the T1 state through the incorporation of bromine atoms at the 2,6-positions does not result in an enhancement of the optical limiting properties on a nanosecond timescale. This suggests that, in contrast with phthalocyanines, access to excited state absorption (ESA) from the T1 state through the introduction of a heavy atom effect does not provide a significantly improved reverse saturable absorbance response compared to ESA from the S1 state.

4-Bis(4-aminophenoxy)phenoxy derivitized phthalocyanine conjugated to metallic nanoparticles: searching for enhanced optical limiting materials

In this study, the photophysical, nonlinear absorption and nonlinear optical limiting properties of 4-(2,4-bis(4-aminophenoxy)phenoxy) phthalocyinato zinc(II) phthalocyanine (6) conjugated to metallic nanoparticles have been investigated using open aperture Z-scan techniques using 532 nm nanosecond pulses. The nonlinear optical response demonstrated that the studied complex and the nanoconjugates exhibit higher excited state absorption cross-section compared to ground state absorption. Enhanced optical limiting performance was observed when complex 6 was conjugated to nanoparticles with 6CB-AuNPs (CB = covalent bond) showing the highest optical limiting threshold of 0.36 J cm−2.

Photophysical and enhanced nonlinear optical response in asymmetric benzothiazole substituted phthalocyanine covalently linked to semiconductor quantum dots

The synthesis of asymmetric benzothiazole substituted phthalocyanines (complexes 3 to 5) and their covalent attachment to glutathione (GSH) functionalized quantum dots (QDs) are reported in this work. Additionally, their photophysical and nonlinear optical properties were investigated. A decrease in the fluorescence quantum yield with corresponding increase in the triplet quantum yield was observed when the complexes were covalently linked to glutathione (GSH) functionalized cadmium telluride (CdTe) quantum dots. Reverse saturable absorption was found to be predominantly dominated by excited state absorption. The observed limiting threshold values range from 0.29-0.75 J/cm2.

Photo-induced resonance energy transfer and nonlinear optical response in ball-type phthalocyanine conjugated to semiconductor and graphene quantum dots

The synthesis of ball-type zinc and gallium phthalocyanines (complexes 2 and 3) and their covalent linkage to glutathione (GSH) and amine functionalized quantum dots (QDs) are reported in this work. Furthermore, their photophysical, photo-induced resonance energy transfer and optical limiting responses were investigated. We observed a decrease in the fluorescence quantum yields with a corresponding increase in the triplet quantum yields of the nanoconjugates in comparison to the phthalocyanine complexes alone. The reverse saturable absorption was found to be dependent on the excited state absorption, and the observed limiting threshold ranged from 0.32 to 1.43 J cm−2. Enhanced triplet parameters and nonlinear optical performance were found when the complexes were covalently linked to semiconductor quantum dots compared to carbon based graphene quantum dots.

The photophysicochemical behavior of symmetric and asymmetric zinc phthalocyanines, surface assembled onto gold nanotriangles

The synthesis of a novel asymmetric phthalocyanine, (4-(4-(benzo[d]thiazol-2-yl)phenoxy)-2,10,17-tris(4-(2-carboxyethyl)phenoxy)phthalocyaninatol)zinc(II), complex 3, is reported. Complex 3 together with the previously reported complexes tetrakis[(benzo[d]thiazol-2-yl phenoxy)phthalocyaninato]zinc(II) (4) and 3-(4-((3,17,23-tris(4-(benzo[d]thiazol-2-yl)phenoxy)phthalocyaninatol)oxy)phenyl)propanoic acid zinc(II) (5), were linked to gold nanotriangles (AuNTs) through S–Au/Au–N self-assembly to afford the conjugates (3-AuNTs, 4-AuNTs and 5-AuNTs). The photophysicochemical behaviour of the complexes and their conjugates were studied. The asymmetric complexes 3 and 5, displayed improved triplet and singlet oxygen quantum yields compared to the symmetric complex 4, while all conjugates displayed improved triplet and singlet oxygen quantum yields compared to their respective complexes alone. The complexes and their conjugates could serve as good candidates for photodynamic therapy.

Novel nano-dyad of homoleptic sandwich-type phthalocyanines with nitrogen doped graphene quantum dots for nonlinear optics

The syntheses of neodymium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (2), bis europium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (3), bis dysprosium(III) 2,9,16,23-tetrakis-(2,6-di-tert-butyl-4-methylphenoxy)phthalocyanine (4) and their conjugated analogues with nitrogen doped quantum dots (NGQDs) are reported herein. The optical nonlinearity of the sandwich-type phthalocyanine complexes and their conjugates with NGQDs were studied in dimethyl sulfoxide using the open aperture Z-scan technique at an excitation wavelength of 532 nm with a 10 ns pulse. The nonlinear absorption coefficient (βeff) value of the samples ranges from 15 cm GW−1 to 89.6 cm GW−1. Complex 4 and its conjugates afforded a strong optical limiting behaviour compared to the other samples. These fabricated complexes and their conjugates with NGQDs could serve as a plausible nonlinear optical (NLO) material due to their fascinating NLO properties.