Photophysical properties of zinc carboxy phthalocyanines-quantum dot conjugates

This thesis presents work based on the interactions of water soluble caboxylated zinc phthalocyanines (Pcs) and coreshell quantum dots (QDs). The Pcs are ZnPc(COOH)₈ and ZnPc(COOH)₄ and coreshell QDs are CdTe@ZnS-GSH. GSH = L-glutathione. Characterization and photophysical studies of conjugates were carried out. The approach of coordinating Pcs to QDs was achieved using an organic cross linker, N-N’-dicyclohexylcarbodiimide (DCC) at pH 10 at room temperature. Employing atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman, infrared and X-ray photoelectron spectroscopies, the formation of the conjugates was confirmed. Upon conjugation with Pc derivatives, the fluorescence quantum yield of CdTe@ZnS-GSH decreased due to energy transfer from the QDs to the Pc. The average fluorescence lifetime of the CdTe@ZnS-GSH QD also decreased upon conjugation. The föster resonance energy transfer (FRET) behaviour of CdTe@ZnS-GSH-ZnPc(COOH)₄ conjugates was compared to that of CdTe@ZnS-GSH-ZnPc(COOH)₈. Higher FRET efficiencies were observed for CdTe@ZnS-GSH-ZnPc(COOH)₄-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₄-linked compared to the corresponding CdTe@ZnS-GSH-ZnPc(COOH)₈-mixed or CdTe@ZnS-GSH-ZnPc(COOH)₈-linked. Triplet quantum yield (ΦT) and lifetime (ΤT) of ZnPc(COOH)₈ were found to increase in the presence of coreshell QDs. Though the singlet quantum yield (ΦΔ) value of ZnPc(COOH)8 was lower than ΦT , there was a slight upsurge in the ΦT in the presence of QDs.Microsoft� Word 2010Adobe Acrobat 9.53 Paper Capture Plug-i

Nonlinear optical behavior of lanthanide phthalocyanines and their conjugates with a selection of nanomaterials

This thesis presents novel asymmetrical and symmetrical lanthanide phthalocyanines (Pcs) characterized using a number techniques including proton nuclear magnetic resonance, electron spin resonance, time correlated single photon counting, FTIR spectrometry, MALDI-TOF mass spectrometry, UV-Vis spectrometry, Raman spectroscopy and CHNS elemental analysis. The design of theses lanthanide Pcs takes the form of mononuclear, binuclear, trinuclear, bis- and tris(phthalocyanines). Nanomaterials such as zinc oxide nanoparticles (ZnO NPs), multi-walled carbon nanotubes (MWCNTs) and graphene oxide nanosheets (GONS) (oxidized and reduced) were employed for covalent linkage to mono- and binuclear phthalocyanines as conjugates. Transmission electron microscopy was used to characterize ZnO NPs, MWCNTs and GONS alone and when linked to lanthanide Pcs. Lanthanide Pcs alone and when linked to ZnO NPs, MWCNTs and GONS where embedded in polymers such as poly (methyl methacrylate) (PMMA), poly (bisphenol A carbonate) (PBC) and poly (acrylic acid) (PAA) for thin film preparation. The thickness of the thin films was determined by utilization of the knife edge attachment of the A Bruker D8 Discover X-ray diffraction (XRD). Optical limiting properties of lanthanide Pcs alone and as conjugates in solution and when incorporated into polymers were determined by employing a Z-scan technique. It emerged that low symmetry lanthanide Pcs (19, 20 and 21), the blue forms of bis(phthalocyanines) (only in solution; 24 and 28) as well as tris(phthalocyanines) (30 and 31) exhibit low limiting threshold (Ilim) values in solution and thin films (particularly PBC and PAA). The low limiting threshold values make these lanthanide Pcs reliable optical limiters

Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines

A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications.Original publication is available at http://dx.doi.org/10.1039/C4TC00505

Electrocatalytic activity of a push-pull phthalocyanine in the presence of reduced and amino functionalized graphene quantum dots towards the electrooxidation of hydrazine

We report on the electrochemical behaviour of reduced graphene quantum dots (rGQDs) compared to amino functionalized graphene quantum dots (NH2GQDs). Reduction of the GQDs entails the elimination of the excessive carboxyl and hydrogen groups on the GQDs surface, thereby reducing the energy band gap. The energy band gap of graphene is directly proportional to the available oxygen atoms. The two GQD types were conjugated to a novel cobalt phthalocyanine (cobalt tris-(tert-butyl phenoxy)-mono-carboxyphenoxy phthalocyanine, CoPc) via covalent and nom-covalent interactions. The resulting conjugates were tested towards the electrooxidation of hydrazine. The conjugates are represented as rGQDs(π)CoPc, NH2(π)CoPc, rGQDs@CoPc and NH2GQDs@CoPc. The resulting conjugates were adsorbed onto a glassy carbon electrode using the drop and dry method. The lowest limit of detection (LOD) was obtained for rGQDs(π)CoPc

The nonlinear absorption in new lanthanide double decker pyridine-based phthalocyanines in solution and thin films

The optical behavior of bis-{2(3), 9(10), 16(17), 23(24)-(tetrapyridin-4-yloxy phthalocyaninato)} lanthanum (III) (2) and its ytterbium (3) counterpart in dimethyl sulfoxide are presented and compared to bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). We report on the third-order susceptibility, second-order hyperpolarizability and the limiting threshold values. The nonlinear optical limiting threshold values of complexes 2, 3 and 4 showed improvement in the solid state (thin films), with complex 4 giving the best value at 0.033 J cm−2.Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.02

The nonlinear absorption in new lanthanide double decker pyridine-based phthalocyanines in solution and thin films

The optical behavior of bis-{2(3), 9(10), 16(17), 23(24)-(tetrapyridin-4-yloxy phthalocyaninato)} lanthanum (III) (2) and its ytterbium (3) counterpart in dimethyl sulfoxide are presented and compared to bis-{1(4), 8(11), 15(18), 22(25)-(tetrapyridin-4-yloxy phthalocyaninato)} ytterbium (III) (4). We report on the third-order susceptibility, second-order hyperpolarizability and the limiting threshold values. The nonlinear optical limiting threshold values of complexes 2, 3 and 4 showed improvement in the solid state (thin films), with complex 4 giving the best value at 0.033 J cm−2.Original publication is available at http://dx.doi.org/10.1016/j.optmat.2015.05.02

Nanosecond nonlinear optical limiting properties of new trinuclear lanthanide phthalocyanines in solution and as thin films

2,4,6-Tris[3-thio-9,10,16,17,23,24-hexa(4-tertbutylphenoxy) phthalocyaninato ytterbium (III) chloride]-s-triazin (3) and its lutetium counterpart (4) were synthesized. The nonlinear optical behavior of 3 and 4 were characterized in solution and when embedded in polymer as thin films. Thin films of complexes 3 and 4 in poly(bisphenol A carbonate) showed improved nonlinear optical properties when compared to solution. Complex 3 showed a lower threshold for optical limiting intensity (Ilim) than complex 4, and for phthalocyanines in general. Ilim values were even lower in films compared to solutions.Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.08.04

Nanosecond nonlinear optical limiting properties of new trinuclear lanthanide phthalocyanines in solution and as thin films

2,4,6-Tris[3-thio-9,10,16,17,23,24-hexa(4-tertbutylphenoxy) phthalocyaninato ytterbium (III) chloride]-s-triazin (3) and its lutetium counterpart (4) were synthesized. The nonlinear optical behavior of 3 and 4 were characterized in solution and when embedded in polymer as thin films. Thin films of complexes 3 and 4 in poly(bisphenol A carbonate) showed improved nonlinear optical properties when compared to solution. Complex 3 showed a lower threshold for optical limiting intensity (Ilim) than complex 4, and for phthalocyanines in general. Ilim values were even lower in films compared to solutions.Original publication is available at http://dx.doi.org/10.1016/j.poly.2014.08.04

Electrochemical and non-linear optical behavior of a new neodymium double-decker phthalocyanine

This manuscript presents the non-linear optical parameters obtained specifically at 532 nm using the new bis-{1(4),8(11),15(18),22(25)-(tetrapyridin-3-yloxy) phthalocyaninato} neodymium(III) complex in green (2a) and blue (2b) forms as well thin films prepared from the green form in the presence of poly(bisphenol A) carbonate. It is interesting to note a huge improvement of the reduction efficiency of transmission of the green form by 34% in poly(bisphenol A) carbonate as a thin film. The same observation is noted for the blue form at 25%. The same trend was observed for the excited state cross sections in which the blue form of the bis-{1(4),8(11),15(18),22(25)- (tetrapyridin-3-yloxy) phthalocyaninato} neodymium(III) complex as well as the thin film exhibited values that were about three and six times greater than those of the green form, respectively. The electrochemical properties were also studied, with complex 2a exhibiting six redox processes in DCM, by employing tetrabutylammonium tetrafluoroborate as an electrolyte

Optical nonlinearities and photophysicochemical behaviour of green and blue forms of lutetium bisphthalocyanines

A rare earth sandwich-type phthalocyanine: bis-{2,3,9,10,16,17,23,24-octa(4-tert-butylphenoxy) phthalocyaninato} lutetium(III) has been synthesized. The photophysical and nonlinear optical behavior of both the “green” and “blue” forms ([LuIIIPc2] and [LuIIIPc2]−, respectively) of the complex have been investigated. High triplet state and singlet oxygen quantum yield values were obtained for the neutral blue form which contains no unpaired electrons. Relatively high third order susceptibility and hyperpolarizability values of the order of 10−10 and 10−28 esu were obtained for both the green and blue forms, respectively. A very low threshold intensity of 0.00051 J cm−2 was obtained for the blue form. Hence the complex shows promise for non-linear optical applications.Original publication is available at http://dx.doi.org/10.1039/C4TC00505