2005
DOI: 10.1139/v05-208
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Abstract: The oxidation of diarylmethanes is a multistep process involving initial formation of a radical cation, deprotonation of the radical cation to the radical, and oxidation of the radical to the carbocation. The dynamics and efficiency of the last two steps in this process, namely deprotonation and oxidation, in acidic zeolites and non-acid zeolites are examined in the present work as a function of the acidity of the diarylmethane radical cations and the oxidation potential of the diarylmethyl radicals. Our resul… Show more

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Cited by 4 publications
(4 citation statements)
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“…5,6 In the past decade, much emphasis has been placed on the use of zeolites as hosts for photoinduced electron transfer (PET) reactions, due to their ability to stabilize charged intermediates. [7][8][9][10][11] Zeolites have also been shown to participate directly in PET reactions, and can behave as oneelectron donors 12,13 or acceptors, [14][15][16] subsequently generating a hole or electron within the aluminosilicate-cation internal structure. While a myriad of reports appear in the literature detailing the individual contributions to the study of zeolites as redox partners, much less emphasis has been placed on determining the fate of the photochemically generated holes and electrons.…”
Section: Introductionmentioning
confidence: 99%
See 1 more Smart Citation
“…5,6 In the past decade, much emphasis has been placed on the use of zeolites as hosts for photoinduced electron transfer (PET) reactions, due to their ability to stabilize charged intermediates. [7][8][9][10][11] Zeolites have also been shown to participate directly in PET reactions, and can behave as oneelectron donors 12,13 or acceptors, [14][15][16] subsequently generating a hole or electron within the aluminosilicate-cation internal structure. While a myriad of reports appear in the literature detailing the individual contributions to the study of zeolites as redox partners, much less emphasis has been placed on determining the fate of the photochemically generated holes and electrons.…”
Section: Introductionmentioning
confidence: 99%
“…Zeolites are crystalline aluminosilicate materials comprised of an open framework of molecular-sized pores, channels, and cavities, enabling guest molecules to be readily adsorbed within their periodic array of void spaces. The presence of tetravalent aluminum in the zeolite framework gives rise to a net negative charge that is typically counterbalanced by protons or alkali metal cations, resulting in a highly polar and strongly ionizing intrazeolite environment. , In the past decade, much emphasis has been placed on the use of zeolites as hosts for photoinduced electron transfer (PET) reactions, due to their ability to stabilize charged intermediates. Zeolites have also been shown to participate directly in PET reactions, and can behave as one-electron donors , or acceptors, subsequently generating a hole or electron within the aluminosilicate-cation internal structure. While a myriad of reports appear in the literature detailing the individual contributions to the study of zeolites as redox partners, much less emphasis has been placed on determining the fate of the photochemically generated holes and electrons.…”
Section: Introductionmentioning
confidence: 99%
“…Diarylmethanes have a rich radical chemistry, with early work showing that radical formation was inherent in the C–C coupling of diarylmethanes to form tetraarylethanes . Neutral diarylmethene radicals have been generated by flash photolysis of diarylmethanes through an oxidation/deprotonation mechanism, and related diarylmethane radical anions have been studied by electron paramagnetic resonance (EPR) spectroscopy. , Importantly, unlike simple diarylmethanes, the heteroatom congeners such as dipyrrins and dipyridyl-, difuryl-, and dithienylmethenes could potentially act as redox-active chelating ligands to transition metals, having some similarity to the well-exploited β-diketiminate ligand family, which has also been shown to exhibit ligand noninnocence. Simple neutral difurylmethene radicals are accessible and have been studied by EPR spectroscopy, and dipyridylmethene complexes of the p-block elements form ligand-radical complexes of varying stability. Because of their relevance to porphyrins and the fluorescent properties of boron-dipyrromethene (BODIPY) dyes and related complexes, dipyrrins have been extensively studied and shown to exhibit redox activity in their complexes and dipyrrin-fullerene triads. Similarly to these studies, we have shown that a simply prepared anionic, imine-expanded dipyrrin acts as a ligand for iron and uranium complexes, the latter showing ligand redox activity . Because of the ligand-based lowest unoccupied molecular orbital (LUMO), the sequential outer-sphere, one-electron reduction of the uranyl­(VI) center to U­(V) and U­(IV) occurs by initial ligand reduction followed by electron transfer to the metal.…”
Section: Introductionmentioning
confidence: 99%
“…16 Diarylmethanes have a rich radical chemistry, with early work showing that radical formation was inherent in the C−C coupling of diarylmethanes to form tetraarylethanes. 17 Neutral diarylmethene radicals have been generated by flash photolysis of diarylmethanes through an oxidation/deprotonation mechanism, 18 and related diarylmethane radical anions have been studied by electron paramagnetic resonance (EPR) spectroscopy. 19,20 Importantly, unlike simple diarylmethanes, the heteroatom congeners such as dipyrrins and dipyridyl-, difuryl-, and dithienylmethenes could potentially act as redox-active chelating ligands to transition metals, having some similarity to the well-exploited β-diketiminate ligand family, which has also been shown to exhibit ligand noninnocence.…”
Section: ■ Introductionmentioning
confidence: 99%