Photophysical characterization of dysprosium, erbium and lutetium phthalocyanines tetrasubstituted with phenoxy groups at non-peripheral positions

Dysprosium bis-phthalocyanine and monomeric phthalocyanines of erbium and lutetium with non-peripheral phenoxy substituents have been synthesized using two different preparative routes. Photophysical studies on these phthalocyanines revealed that the triplet states of dysprosium and erbium are not populated while the monomeric phthalocyanine complex of lutetium is populated with a quantum yield of 0.83 and a lifetime of 25 μs in DMSO. It was further found that the phthalocyanine complex of lutetium was capable of photochemical generation of singlet state molecular oxygen with yield of 0.71 in THF, thus a promising photosensitizer. However, the three phthalocyanine molecules have very low fluorescence quantum yields of less than 0.01

Fluorescence Behaviour of an Aluminium Octacarboxy Phthalocyanine-NaYGdF 4

Using a methanol assisted thermal decomposition approach, sphere shaped NaYGdF4:Yb/Er upconversion nanoparticles (UCNPs) were successfully synthesized. The chemical, spectroscopic and fluorescence properties of the UCNPs were fully characterized. Characteristic upconversion fluorescence emissions were produced by the NPs in the green, red and NIR regions and the NPs were also shown to possess paramagnetic properties. The influence of the UCNPs on the spectroscopic and fluorescence properties of an aluminium octacarboxy phthalocyanine AlOCPc was investigated. Covalent conjugation to an AlOCPc resulted in a large blue shift of the phthalocyanine’s Q band, which was accompanied by a decrease in the Pc’s fluorescence lifetime in DMSO. By combining the phthalocyanine and upconversion nanoparticle, we present a system capable of multimodal imaging, using both the upconversion nanoparticle’s and phthalocyanine’s emission, and magnetic resonance imaging (as a result of doping the upconversion nanoparticles with Gd3+ ions)

Synthesis and characterization of Na (Y, Gd) F4 upconversion nanoparticles and an investigation of their effects on the photophysical properties of an unsubstituted tetrathiophenoxy phthalocyanine

Sphere- and star-shaped Na(Y,Gd)F4:Yb/Er(Tm)upconversion nanoparticles (UCNP) were successfully synthesized utilizing a methanol-assisted thermal decomposition approach and their spectroscopic (absorption, emission and luminescence lifetime) properties fully characterized. The factors affecting the size and shape of the UCNPs were studied and discussed in detail. The size of the nanoparticles was determined using TEM primarily and found to be approximately 19 and 30 nm for the Er and Tm spheres, respectively, while the Er and Tm “stars” were found to be much larger with sizes ranging from 110 to 240 nm, respectively (as determined along the width of the nanoparticle). In addition, their influence on the spectroscopic properties of an unsubstituted tetrathiophenoxy phthalocyanine (H2Pc) was investigated. The UCNP were found to produce characteristic upconversion luminescence emissions in the blue, green, red and NIR regions. Simple mixing with an H2Pc in toluene was found to exert no obvious changes in the spectroscopic properties of the Pc, although a considerable increase in the radiative lifetimes is observed for the Pc in the presence of the UCNPs. The singlet oxygen generation mediated by the red light excitation of the H2Pc mixed with UCNP was found to decrease in the presence of the NPs

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

The synthesis and characterisation of magnetic nanoparticles and their interaction with a zinc phthalocyanine

A variety of nanoparticles (NPs), including FePt nanoparticles with Fe as the shell (2) or Pt as the shell (3), Pt NPs (4), and FePd (5) were synthesised, characterised and their effect on a zinc phthalocyanine (1) tetra-substituted with a pyridyl-oxy substituent studied using UV/Vis and fluorescence spectroscopy (including time correlated single photon counting, TCSPC). The nanoparticles were characterised using a number of techniques including UV/Vis and inductively coupled plasma-optical emission (ICP-OES) spectroscopies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and electron paramagnetic resonance (EPR) spectroscopy. Nanocomposites (NCs, 6,7) where the ZnPc (1) was used as the stabiliser, instead of oleic acid and or oleylamine, were also synthesised and characterised

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

Catalytic oxidation of thioanisole using oxovanadium (IV)‐functionalized electrospun polybenzimidazole nanofibers

Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts

Ultrafast Photodynamics of the Indoline Dye D149 Adsorbed to Porous ZnO in Dye‐Sensitized Solar Cells

We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I−/I3− redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns