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71.
Spectroscopic studies were carried out on the homoaggregates of negatively charged free base meso-tetraphenylsulfonated porphyrin ([H2TPPS4]4−) and heteroaggregates of a mixture of protonated ([H4TPPS4]2−) and tin meso-tetra (N-methyl-4-pyridyl) porphyrin ([SnTMPyP]4+). The spectroscopic studies were done to determine the optimal conditions required for the fabrication of porphyrin nanorods by ionic self assembly of two oppositely charged porphyrins. In addition, the various spectral changes of [H4TPPS4]2− with concurrent change in pH and concentration are also investigated. In acid media at pH <3, and at concentrations >1 × 10−5 M, [H4TPPS4]2− molecules form J aggregates. A mixture of [H4TPPS4]2− and [SnTMPyP]4+ forms heteroaggregates of the J type in acid media. At pH’s 2 to 3, the optimum ratio for the formation of J aggregates is 3:1 and for pH 1, the optimum ratio is 2:1. Transmission electron microscope images of the nanostructures formed show that they are of cylindrical shape. 相似文献
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73.
Reama C.George Tawanda Mugadza Samson Khene Gabriel O. Egharevba Tebello Nyokong 《Electroanalysis》2011,23(7):1699-1708
Porphyrin nanorods (PNR) were prepared by ionic self‐assembly of two oppositely charged porphyrin molecules consisting of free base meso‐tetraphenylsulfonate porphyrin (H4TPPS42?) and meso‐tetra(N‐methyl‐4‐pyridyl) porphyrin (MTMePyP4+M=Sn, Mn, In, Co). These consist of H4TPPS42?? SnTMePyP4+, H4TPPS42?? CoTMePyP4+, H4TPPS42?? InTMePyP4+ and H4TPPS42?? MnTMePyP4+ porphyrin nanorods. The absorption spectra and transmission electron microscopic (TEM) images of these structures were obtained. These porphyrin nanostructures were used to modify a glassy carbon electrode for the electrocatalytic reduction of oxygen, and the oxidation of hydrazine and methanol at low pH. The cyclic voltammogram of PNR‐modified GCE in pH 2 buffer solution has five irreversible processes, two distinct reduction processes and three oxidation processes. The porphyrin nanorods modified GCE produce good responses especially towards oxygen reduction at ?0.50 V vs. Ag|AgCl (3 M KCl). The process of electrocatalytic oxidation of methanol using PNR‐modified GCE begins at 0.71 V vs. Ag|AgCl (3 M KCl). The electrochemical oxidation of hydrazine began at around 0.36 V on H4TPPS42?? SnTMePyP4+ modified GCE. The GCE modified with H4TPPS42?? CoTMePyP4+ H4TPPS42?? InTMePyP4+ and H4TPPS42?? MnTMePyP4+ porphyrin nanorods began oxidizing hydrazine at 0.54 V, 0.59 V and 0.56 V, respectively. 相似文献
74.
We described the synthesis of nickel octadecylphthalocyanine (NiPc(C10H21)8), followed by its adsorption on single‐walled carbon nanotubes (SWCNT) to form SWCNT‐NiPc(C10H21)8 conjugates. SWCNT‐NiPc(C10H21)8 was used to modify a glassy carbon electrode (GCE) and for the electrooxidation of 4‐chlorophenol and 2,4‐dichlorophenol. The SWCNT and NiPc(C10H21)8 have a synergistic effect on each other in terms of improving electrocatalysis for the detection of chlorophenols. The stability of the electrode improved in the presence of NiPc(C10H21)8 or NiPc compared to the bare GCE. The presence of SWCNT improves the electrocatalytic behaviour of NiPc(C10H21)8 but not of unsubstituted NiPc. All modified electrodes showed improved stability towards the detection of 2,4‐dichlorophenol. The best stability for 4‐CP detection was observed in the presence of SWCNT for NiPc(C10H21)8. 相似文献
75.
The syntheses of new ball-type Co(II) phthalocyanines containing 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at non-peripheral (complex 6) and peripheral (complex 7) positions are presented. These complexes were characterized by UV-Vis, FT-IR, mass spectroscopy and electrochemical methods. Both complexes exhibit metal and ring based redox processes, typical of cobalt phthalocyanine complexes. For 6, the metal based reduction was observed at −0.46 V followed by a ring based reduction at −1.40 V. The metal oxidation for 6 was observed at +0.16 V and the ring based oxidation at +1.05 V. For 7, reductions are easier but the oxidations are more difficult. The metal based reduction for 7 was observed at −0.38 V followed by a ring based reduction at −1.03 V. The metal oxidation for 7 was observed at +0.20 V and the ring based oxidation at +1.35 V. 相似文献
76.
The syntheses of 2,(3)-(peripheral) and 1,(4)-(non-peripheral) (2-mercaptopyridine)phthalocyanine complexes of titanium(IV) oxide (5a and 6a, respectively), vanadium(IV) oxide (7a and 8a, respectively) and tantalum(V) hydroxide (9a, peripheral only) and their electrochemical characterization are presented in this report. Their electrochemistry is compared to that of thiophenyl and thiobenzyl substituted derivatives. The non-peripherally substituted complexes are more difficult to reduce than peripherally substituted derivatives. In addition, the mercaptopyridine substituted derivatives are more difficult to reduce compared to benzylmercapto and phenylmercapto derivatives, and aryl easier reduce than alkyl substitution. Spectroelectrochemistry of the complexes confirmed metal and ring redox processes for TaPc and TiPc derivatives and ring based processes only for VPc complexes. 相似文献
77.
The effects of solvents on the singlet oxygen, photobleaching and fluorescence quantum yields for zinc phthalocyanine (ZnPc) and its derivatives; (pyridino)zinc phthalocyanine ((py)ZnPc), zinc octaphenoxyphthalocyanine (ZnOPPc) and zinc octaestronephthalocyanine (ZnOEPc), is presented. The effects of the solvents on the ground state spectra are also discussed. The largest red shift of the Q band was observed in aromatic solvents, the highest shift being observed for 1-chloronaphthalene. Higher singlet fluorescence quantum yields were observed in THF for ZnPc and ZnOPPC. Also in the same solvent phototransformation rather than photobleaching was observed for ZnOPPc. Split Q band in the emission and excitation spectra of ZnOPPc was observed in some solvents and this is explained in terms of the lowering of symmetry following excitation. 相似文献
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79.
This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.80 to 0.86 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and <10 μs in the rest of the solvents) were observed due to the presence of heavy atom. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm2. 相似文献
80.
Kenneth I. Ozoemena Solomon A. Mamuru Takamitsu Fukuda Nagao Kobayashi Tebello Nyokong 《Electrochemistry communications》2009,11(6):1221-1225
Novel hexabutylsulphonyltribenzotetraazachlorin–fullerene (C60) complexes of iron (FeHBSTBTAC–C60) and cobalt (CoHBSTBTAC–C60) have been synthesized and their electrochemistry and oxygen reduction reaction (ORR) compared with their octabutylsulphonylphthalocyanine analogues (FeOBSPc and CoOBSPc). It is proved that electron-withdrawing substituents (–SO2Bu and C60) on phthalocyanine macrocycle exhibit distinct impact on the solution electrochemistry of these metallophthalocyanine (MPc) complexes. The more electron-withdrawing C60 substituent suppressed ORR compared to the –SO2Bu in alkaline medium. FeOBSPc showed the best ORR activity involving a direct 4-electron mechanism, a rate constant of ~1 × 108 cm3 mol?1 s?1 and a Tafel slope of ?171 mV dec?1. 相似文献