Catalytic activity of noble metal ions for the degradation of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphine in the presence of oxidizing agent, and its application to the determination of ultra trace amounts of ruthenium

Kawamura, Kunio; Igarashi, Shukuro; Yotsuyanagi, Takao

doi:10.1007/s00604-010-0489-8

Cited by 7 publications

(4 citation statements)

References 21 publications

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“…for mercury(II) [31], other post-transition metal ions (Cd 2+ , Zn 2+ , Pb 2+ , Cu 2+ ) [32], manganese(II) and (III) [33], cobalt(II) (using photolabile cadmium(II) porphyrin) [34]. For detection of platinoid metal ions in trace amounts, an indirect spectrophotometric process was developed by the degradation of water-soluble porphyrins in the reaction with oxidants, catalysed by noble metal ions [35,36]. Several fluorometric procedures are widely used, e.g.…”

Section: Analytical Applications Of Porphyrinsmentioning

confidence: 99%

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Application of the electronic spectra of porphyrins for analytical purposes: The effects of metal ions and structural distortions

Valicsek

Horváth

2013

Microchemical Journal

126

118

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We investigated the UV-Vis absorption, singlet-1 and singlet-2 fluorescence, as well as the formation of several metalloporphyrins from equilibrial and kinetic aspects in aqueous solution. Among these complexes were numerous typical out-of-plane and several in-plane metalloporphyrins, and between the two categories, a few border-line cases. On the basis of our results, we have complemented the categorization introduced by Barnes and Dorough for the metalloporphyrins. According to our observations, also in metalloporphyrins, the distortion, i.e., the planarity or nonplanarity of the macrocycle, is basically responsible for the spectral characteristics, while the electronic structure of metal center is a secondary factor, with a considerable importance mainly in the in-plane complexes. The type of complexes can be spectrophotometrically determined on the basis of their UV-Vis absorption and fluorescence spectra. Beside the spectral and photophysical effects of metalation, also those of the structural distortions were studied, which can originate also from metalation, protonation or overcrowded peripheral substitution of the free-base porphyrins, as well as from the axial ligation of metalloporphyrins. Our observation may be useful for different spectrophotometric analytical detection and determination methods, e.g. size-selective metal detection using free-base porphyrins (or other ringed chelate ligands), as well as the determination of Lewis bases as potential axial ligands, using metalloporphyrins.

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Section: Analytical Applications Of Porphyrinsmentioning

confidence: 99%

“…5) because its negative charge enhances the coordination of positively charged metal ions. Furthermore, this ligand is the most widely used analytical reagent among the porphyrin derivatives [28,35,36,42,59,60,65]. However, our spectrophotometric conclusions can be adapted for other porphyrins too.…”

Section: Analytical Applications Of Porphyrinsmentioning

confidence: 99%

Application of the electronic spectra of porphyrins for analytical purposes: The effects of metal ions and structural distortions

Valicsek

Horváth

2013

Microchemical Journal

126

118

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“…Metalloporphyrins play key roles in numerous biochemical processes, such as photosynthesis and oxygen transport as well as in various redox reactions. [1][2][3][4][5][6][7][8] Within this important group of compounds, the so-called out-of-plane (OOP) or sitting-atop (SAT) metalloporphyrins show special properties, [9][10][11][12] which originate from the non-planar structure caused by, first of all, the size of the metal center. In these complexes, the ionic radius (>80-90 pm) of the metal center is too large to fit into the cavity of the ligand, therefore it is located above the porphyrin plane, distorting it.…”

Section: Introductionmentioning

confidence: 99%

Equilibrium, photophysical and photochemical examination of anionic lanthanum(iii) mono- and bisporphyrins: the effects of the out-of-plane structure

2012

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Lanthanum(III) ion forms kinetically labile complexes with the 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin anion (H2TSPP 4-), the compositions and formation constants of which significantly depend on the presence of potential axial ligands (at 0.01 M). Deviating from the chloride ion, acetate coordinating to the metal center hinders the formation of bisporphyrin complex. In these 10 lanthanum(III) complexes, the metal center, due to its large ionic radius (103.2 pm), is located out of the ligand plane, distorting it. Accordingly, the absorption and fluorescence spectra of these coordination compounds display special properties characteristic of the so-called sitting-atop (SAT) or out-of-plane (OOP) porphyrin complexes. Metalation significantly decreases the quantum yield of the fluorescence from the S1 excited state. Quantum chemical calculations (DFT) confirm the considerable OOP 15 displacement of the La(III) center (about 120 pm in the monoporphyrin complexes). The monoporphyrins display efficient fluorescence (0.03), while the bisporphyrin does not emit. Differing from the normal (in-plane) metalloporphyrins, excitation of these lanthanum(III) porphyrins leads to an irreversible ligandto-metal charge transfer (LMCT) followed by the opening of the porphyrin ring, which is also typical of OOP complexes. Dissociation releasing free-base porphyrin can also be observed upon irradiation of the 20 monoporphyrin in acetate solution, while in the presence of chloride ions interconversions of the monoand bisporphyrins may also take place beside the irreversible photoredox reaction.

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“…[1][2][3][4][5][6][7][8][9] In addition, metal-porphyrin complexes have various functions that are useful in analytical chemistry, and are also of interest to many other researchers, which has led to the use of metal-porphyrin complexes in applications such as optics, 10 chemical stacking, 11 catalysis, 12 electron transport, 13 oxidation-reduction reactions, 14 and biological mimicking substances. 15,16 Thus, numerous reports regarding the chemical function and applications of porphyrin derivatives have been published.…”

Section: Introductionmentioning

confidence: 99%

β-Cyclodextrin as a Metal-anionic Porphyrin Complexation Accelerator in Aqueous Media

et al. 2016

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Catalytic activity of noble metal ions for the degradation of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphine in the presence of oxidizing agent, and its application to the determination of ultra trace amounts of ruthenium

Cited by 7 publications

References 21 publications

Application of the electronic spectra of porphyrins for analytical purposes: The effects of metal ions and structural distortions

Application of the electronic spectra of porphyrins for analytical purposes: The effects of metal ions and structural distortions

Equilibrium, photophysical and photochemical examination of anionic lanthanum(iii) mono- and bisporphyrins: the effects of the out-of-plane structure

β-Cyclodextrin as a Metal-anionic Porphyrin Complexation Accelerator in Aqueous Media

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