Jonathan Britton

Optical limiting behavior of ring substituted zinc, indium and gallium phthalocyanines in the presence of quantum dots

This paper presents the study of the effects of CdTe-TGA quantum dots (QDs) on optical limiting ability of different phthalocyanine (Pc) complexes (1–10) containing Zn, Ga, In central metals and substituted with benzyloxyphenoxy, phenoxy, tert-butylphenoxy and amino groups. The optical limiting parameters of Pcs were higher for tert-butylphenoxy when compared to benzyloxyphenoxy and phenoxy substituents, in DMSO. Non-peripheral substitution decreased the optical limiting parameters. Third-order susceptibility (Im[χ(3)]/α) values of Pcs in the absence and presence of CdTe QDs were in the 10-12 to 10-10 esu.cm range. Hyperpolarizabilities (γ) ranged from 10-31 to 10-29 esu L for Pc alone or in mixture with QDs. There is a general improvement in optical limiting ability of Pc complexes in the presence of CdTe TGA QDs. Due to these promising results, future work can be implemented for the creation of Pc:QD thin films, which would then be examined to ensure that their optical limiting ability is still acceptable.

Third order nonlinear optical properties of phthalocyanines in the presence nanomaterials and in polymer thin films

Third order nonlinear optical properties were determined for phthalocyanine complexes 1–10 containing In, Ga and Zn central metals and tetra- or octa-substituted with benzyloxyphenoxy, phenoxy, tert-butylphenoxy and amino groups at peripheral or non-peripheral positions. The phthalocyanines were embedded in poly (methyl methacrylate) polymer in the presence of CdTe quantum dots. All complexes 1–10 were studied in the presence of CdTe quantum dots and embedded in poly (methyl methacrylate) to form thin films. Complex 3 tetrasubstituted with tert-butylphenoxy groups at non-peripheral positions was also studied in the presence of CdS, CdSe quantum dots, fullerenes, single walled carbon nanotubes. Third order nonlinear optical parameters generally increase for Pcs in the presence of CdTe quantum dots.

Optical Limiting Analysis of Phthalocyanines in Polymer Thin Films

This paper reports on the effect of embedding twelve phthalocyanines containing In, Ga, Zn and Al as central metals in polymer thin films on their optical limiting abilities. This paper also examines the effect of forming a covalent link between zinc tetraamino phthalocyanine (10) and poly (methyl acrylic acid) (PMAA), and Zn (11) or OHAl (12) octacarboxy phthalocyanines with polyethylenimine (PEI). The average film thickness (for phthalocyanines mixed or linked to polymers) of each Pc/Polymer films on glass was 95 μm. The hyperpolarizability of the twelve phthalocyanines was found to be in the range of 10−26 to 10−24 esu.L. This is significantly higher than the hyperpolarizabilities of these phthalocyanines in solution, which ranged from 10−30 to 10−26 esu.L. Degradation studies seem to indicate that placing a phthalocyanine within a polymer thin film may protect it slightly from photo- and thermal degradation.

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.

Spectroscopic and nonlinear optical properties of the four positional isomers of 4α-(4-tert-butylphenoxy)phthalocyanine

The spectroscopic and nonlinear optical properties of the positional isomers of metal free 4α-(4-tert-butylphenoxy) phthalocyanine are presented. Second order nonlinear polarizability (β), imaginary hyperpolarizability (Im(γ)) and imaginary susceptibility (Im[χ(3)]) values were determined for the four positional isomers. The measured β values of the four isomers displayed the following trend, C4h (34.0 × 10−5 m MW−1) > D2h (28.8 × 10−5 m MW−1) > C2v (22.8 × 10−5 m MW−1) > Cs (13.7 × 10−5 m MW−1).

Improvement of nonlinear optical properties of phthalocyanine bearing diethyleneglycole chains: Influence of symmetry lowering vs. heavy atom effect

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-n-butoxyphthalocyanine 1H2 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 1H2 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)]/α, βeff, and γ for 1H2in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)]/α values of the order of 10−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H2 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)]/α was almost three times higher in comparison with 1H2 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiation.

Improving singlet oxygen generating abilities of phthalocyanines: aluminum tetrasulfonated phthalocyanine in the presence of graphene quantum dots and folic acid

Abstract Glutathione-capped graphene quantum dots (GQDs@GSH) were covalently linked to folic acid (FA). Aluminum tetrasulfonated phthalocyanine (ClAlTSPc) was then adsorbed on the GQDs@GSH-FA conjugate to form GQDs@GSH-FA/ClAlTSPc or on GQDs@GSH and pristine GQDs alone to form GQDs@GSH/ClAlTSPc and GQDs/ClAlTSPc, respectively. We report for the first time on the photophysicochemical behavior of the resulting nanoconjugates. The fluorescence quantum yields of pristine GQDs, GQDS@GSH, or GQDs@GSH-FA conjugate were quenched upon non-covalent interaction (π–π) with ClAlTSPc. There was an increase in triplet quantum yields from 0.38 for ClAlTSPc alone to 0.60, 0.75, and 0.73 when ClAlTSPc was linked to pristine GQDs, GQDs@GSH, and GQDs@GSH-FA, respectively. The singlet oxygen quantum yields also increased from 0.37 for ClAlTSPc alone to 0.42 (for ClALTSPc with pristine GQDs), 0.52 (for ClAlTSPc with GQDs@GSH), and 0.54 (for ClAlTSPc with GQDs@GSH-FA). Thus, the present work may lead to a new generation of carbon-based nanomaterial photodynamic therapy agents with overall performance superior to conventional agents in terms of singlet oxygen generation, water dispersibility, and biocompatibility.

Effects of pluronic silica nanoparticles on the photophysical and photodynamic therapy behavior of triphenyl-p-phenoxy benzoic acid metalloporphyrins

Abstract 5, 10, 15, Triphenyl-20-p-phenoxy benzoic acid porphyrins (P) containing Zn (ZnP), Ga (GaP), and Si (SiP) were synthesized and conjugated to pluronic-silica (PluS) nanoparticles (NPs) where the fluorescence and singlet oxygen generating behavior of the porphyrins were investigated. The highest singlet oxygen quantum yield (ΦΔ) was obtained for ZnP. When the porphyrins were conjugated to the PluS NPs, the ΦΔ was quenched and fluorescence was enhanced. The pore size of the NPs upon conjugation decreased from 18.9 nm for PluS NPs to 2.4 nm (for ZnP as an example) as determined by applying the Brunauer–Emmett–Teller method. The porphyrin complexes and their conjugates were tested for their photodynamic therapy (PDT) activity on MCF-7 breast cancer cells. It was found that ZnP and its conjugate showed the highest PDT activity. The p > 0.05 indicated that ZnP is significantly different than GaP and SiP. Graphical Abstract

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

Optical limiting and singlet oxygen generation properties of phosphorus triazatetrabenzcorroles

Novel phosphorus triazatetrabenzcorrole (TBC) tetrasubstituted at the α- and β-positions of the peripheral fused benzene rings with t-butylphenoxy substituents have been prepared and characterized. The effect of the substituents on the electronic structures and optical properties is investigated with TD-DFT calculations and MCD spectroscopy. The optical limiting properties have been investigated to examine whether the lower symmetry that results from the direct pyrrole–pyrrole bond and hence the permanent dipole moment that is introduced result in higher safety thresholds, relative to the values that have been reported for phthalocyanines. The suitability of the compounds for singlet oxygen applications has also been examined.