Structural, electrochemical and photochemical investigation of the water-soluble tin(IV) tetrakis(2-N-hydroxyethyl-4-pyridinium)porphyrin photocatalyst

Olijve, Luuk L. C.; How, Ethan N. W.; Bhadbhade, Mohan; Prasad, S. Shibu; Colbran, Stephen B.; Zhao, Chuan; Thordarson, Pall

doi:10.1142/s1088424611004312

Cited by 9 publications

(4 citation statements)

References 24 publications

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“…These spectral features were previously attributed to π-radical anion and/or phlorin by different authors or overlapping of the spectral features of these species. 20,41,45,[51][52][53][54]84,89,113,114 Moreover, both π-radical anion and phlorin are easily oxidized by oxygenation, resulting in the disappearance of their spectral features. Therefore, currently, we have no reliable data to attribute these spectral features specifically either to π-radical anion or phlorin.…”

Section: Resultsmentioning

confidence: 99%

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Influence of Meso-Substitution of the Porphyrin Ring on Enhanced Hydrogen Evolution in a Photochemical System

et al. 2016

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This study establishes the relationships between the structure of a series of meso-substituted tin(IV) porphyrins and their efficiency as photosensitizers for hydrogen generation in the Sn(IV)P/Pt–TiO2 nanocomposite system. The electrochemical properties of a series of SnPs, the catalytic performance of Pt nanomodifications, and the morphology of the Pt/TiO2 nanocomposites were characterized by electrochemical and electron microscopy methods. The dependence of photocatalytic performance on the structure for a series of Sn(IV) meso-substituted phenyl porphyrins was studied, and possible mechanisms are discussed employing the results of the electrochemical studies. It was found that the time course and type of the photochemically reduced species of Sn(IV)Ps, which are essential intermediates, are important factors and depend on the electronegativity of the metal center, the character of meso-substituents of the porphyrin ring, and pH and are correlated with the redox potential sequence of the respective Sn(IV)Ps: SnTMPyP > SnTPyP > SnTPPS > SnTPPC. Optimization of the experimental parameters was performed with regard to the SnPs with different functional groups, pH values, concentrations of Pt/TiO2, light intensity, and Pt nanoparticles with different surface stabilizers. Finally, the maximum hydrogen yield under visible light was obtained from the system of Sn(IV) meso-tetra(4-pyridyl)porphyrin dichloride (SnTPyP) sensitized TiO2/Pt prepared by the citrate method/EDTA at pH 9.0. This demonstrates that the photochemically reduced species of SnTPyP are relatively long lived, so they have enough time to complete electron transfer to TiO2 and/or Pt. The adsorption of SnTPyP on the TiO2/Pt surface is therefore not essential for hydrogen generation. Moreover, this study demonstrates for the first time the synergic effect of the excitation of TiO2 and mostly Q-bands of Sn(IV)P (wavelength range 390–650 nm), which enhances the efficiency of photocatalytic hydrogen generation in the system. The Soret band of Sn(IV)TPyP was found to produce a minor (about 23%) contribution to the photocatalytic activity of the porphyrin sensitizer in this system. Possible processes involved are discussed, and mechanisms are proposed explaining different aspects of a series of photocatalytic systems with SnPs and Pt catalysts for hydrogen production under visible light. These structure–function relationships are essential to effectively harness solar energy for hydrogen production as well as for a wide range of energy and environmentally related problems.

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Section: Resultsmentioning

confidence: 99%

“…It was not possible to detect oxidation potentials for the latter porphyrins since they are oxidized at higher potentials, which is in agreement with ref . Additionally, possible impurities in the porphyrin samples and dimerization of pyridinium groups (SnTMPyP) might be responsible for some features on complex CVs of Figure .…”

Section: Resultsmentioning

confidence: 99%

Influence of Meso-Substitution of the Porphyrin Ring on Enhanced Hydrogen Evolution in a Photochemical System

et al. 2016

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“…The photocatalysis of the Pt 2+ and Au + reduction leads to form of nanostructures. [105,106] The mechanism of the photocatalytic reactions of the main group porphyrin/phthalocyanine complexes remains the actual task; using photocatalytic experiment on tin(IV) porphyrin under anaerobic conditions with triethanolamine as a sacrifical donor, the authors [107] have shown that tin(IV) porphyrin π-radical anion is perhaps not the species responsible for the apparent ability tin(IV) porphyrins to photocatalytically reduce substrates.…”

Section: The Main Group Porphyrin/phthalocyanine Complexes As Catalystsmentioning

confidence: 99%

The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

Ломова¹

2021

MHC

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The article is the short review of the recent works in the physical and applied chemistry of the main group porphyrin complexes. Several classic articles on the topic are included in the discussion. Special attention is paid to the specificity of preparation methods, with the demonstration of the specific original syntheses, as well as of optical properties, reactivity and new applications. The prospects of the main group porphyrin complexes in medicine, catalysis, and optoelectronics are briefly presented.

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“…There are a number of common structural and topological features that have been observed in architectures containing TPyP which are dictated by its rigidity and self-complementarity. These features include a variety of one-dimensional chains, ,− two-dimensional nets based on the (4, 4) topology ,,− which can be cross-linked into three-dimensional networks, − and three-dimensional architectures including the NbO, ,− CdSO 4 , , PtS, face-centered cubic, and α-polonium nets . Further, the architectures that have been encountered include a large number of potentially porous networks, often containing disordered solvent molecules. − The range of architectures expands when TPyP is combined with noncovalently bound coformers.…”

Section: Introductionmentioning

confidence: 99%

Structural Diversity in Tetrakis(4-pyridyl)porphyrin Supramolecular Building Blocks

Mishra

Choudhary

Cordes

et al. 2019

Crystal Growth & Design

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In memory of a pioneer in crystal engineering, Prof. Israel Goldberg, we report a series of new framework solids, based on the ligand tetrakis(4-pyridyl)porphyrin (TPyP). Spontaneous reactions of TPyP with seven different metal salts under liquid-liquid diffusion at ambient temperature show that the formation of ionic compounds is preferred to coordination polymers due to increased conformational freedom. Two coordination networks, {(HgI2)2(TPyP)}n•4nCHCl3•2nTCE (TCE = 1,1,2,2-tetrachloroethane), and {(Ba(μ1,1-NCS)(μ1,1,3-NCS)(H2O)(MeCN))2(TPyP)}n•4nH2O, displayed a new isomeric form of the known [(HgI2)2(TPyP)]∞ polymeric motif, and a two-2 dimensional honeycomb polymeric motif linked by hydrogen-bonding into a three dimensional moganite (mog) net, respectively. Four protonated porphyrinic salts, [H3TPyP][PF6]3•0.5TCE, [H2TPyP][I3]2•2MeOH, [H4TPyP][UO2Cl4]2•6MeCN, and [H4TPyP][Th(NO3)6][NO3]2, were observed which hydrogen bond to give one-or two-dimensional networks, or in the case of [H4TPyP][UO2Cl4]2•6MeCN, a discrete dinuclear hydrogen-bonded complex. In one case, a neutral, hydrogen-bonded complex, Ce(NO3)3(MeOH)3(H2O)•TPyP•TCE•H2O, was formed which adopts a three-dimensional, self-penetrated variant of the face-centered cubic (fcc) network. These new structures represent hybrid organic-inorganic crystalline compounds in which the multidentate porphyrin units, having both hydrogen bonding, as well as coordination functionalities, are interlinked through the inorganic connectors into self-assembled three-dimensional architectures.This work shows the relative stability of noncovalently bound vs. coordination networks as well as the effective potential of the TPyP building block to construct supramolecular assemblies in the presence or absence of coordinating ions as linkers.

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Structural, electrochemical and photochemical investigation of the water-soluble tin(IV) tetrakis(2-N-hydroxyethyl-4-pyridinium)porphyrin photocatalyst

Cited by 9 publications

References 24 publications

Influence of Meso-Substitution of the Porphyrin Ring on Enhanced Hydrogen Evolution in a Photochemical System

Influence of Meso-Substitution of the Porphyrin Ring on Enhanced Hydrogen Evolution in a Photochemical System

The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

Structural Diversity in Tetrakis(4-pyridyl)porphyrin Supramolecular Building Blocks

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