Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism

We report an efficient triplet state self-quenching mechanism in crystals of eight benzophenones, which included the parent structure (1), six 4,4′-disubstituted compounds with NH 2 (2), NMe 2 (3), OH (4), OMe (5), COOH (6), and COOMe (7), and benzophenone-3,3′,4, 4′-tetracarboxylic dianhydride (8)....

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Autores principales:	Kuzmanich, G., Simoncelli, S., Gard, M.N., Spänig, F., Henderson, B.L., Guldi, D.M., Garcia-Garibay, M.A.
Formato:	JOUR
Materias:	Crystalline solids Diffusion limited Disubstituted compounds Electron-rich Excited state kinetics Femtoseconds Iodide ion Nanocrystallines Nanosecond transient absorption Orders of magnitude Parent structure Phosphorescence lifetime Quenching mechanisms Self-quenching Self-quenching effect Triplet quenching Triplet state Charge transfer Crystal structure Crystals Excited states Ion exchange Polypropylenes Rate constants Quenching 4,4' bis(dimethylamino)benzophenone 4,4' diaminobenzophenone 4,4' dihydroxybenzophenone benzophenone derivative iodide nanocrystal unclassified drug article chemical reaction kinetics chemical structure crystal structure molecular dynamics phosphorescence purification self quenching synthesis Benzophenones Kinetics Nanoparticles Oxidation-Reduction Particle Size Surface Properties
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_00027863_v133_n43_p17296_Kuzmanich
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

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spelling	todo:paper_00027863_v133_n43_p17296_Kuzmanich2023-10-03T13:54:18Z Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism Kuzmanich, G. Simoncelli, S. Gard, M.N. Spänig, F. Henderson, B.L. Guldi, D.M. Garcia-Garibay, M.A. Crystalline solids Diffusion limited Disubstituted compounds Electron-rich Excited state kinetics Femtoseconds Iodide ion Nanocrystallines Nanosecond transient absorption Orders of magnitude Parent structure Phosphorescence lifetime Quenching mechanisms Self-quenching Self-quenching effect Triplet quenching Triplet state Charge transfer Crystal structure Crystals Excited states Ion exchange Polypropylenes Rate constants Quenching 4,4' bis(dimethylamino)benzophenone 4,4' diaminobenzophenone 4,4' dihydroxybenzophenone benzophenone derivative iodide nanocrystal unclassified drug article chemical reaction kinetics chemical structure crystal structure molecular dynamics phosphorescence purification self quenching synthesis Benzophenones Kinetics Nanoparticles Oxidation-Reduction Particle Size Surface Properties We report an efficient triplet state self-quenching mechanism in crystals of eight benzophenones, which included the parent structure (1), six 4,4′-disubstituted compounds with NH 2 (2), NMe 2 (3), OH (4), OMe (5), COOH (6), and COOMe (7), and benzophenone-3,3′,4, 4′-tetracarboxylic dianhydride (8). Self-quenching effects were determined by measuring their triplet-triplet lifetimes and spectra using femtosecond and nanosecond transient absorption measurements with nanocrystalline suspensions. When possible, triplet lifetimes were confirmed by measuring the phosphorescence lifetimes and with the help of diffusion-limited quenching with iodide ions. We were surprised to discover that the triplet lifetimes of substituted benzophenones in crystals vary over 9 orders of magnitude from ca. 62 ps to 1 ms. In contrast to nanocrystalline suspensions, the lifetimes in solution only vary over 3 orders of magnitude (1-1000 μs). Analysis of the rate constants of quenching show that the more electron-rich benzophenones are the most efficiently deactivated such that there is an excellent correlation, ρ = -2.85, between the triplet quenching rate constants and the Hammet θ + values for the 4,4′ substituents. Several crystal structures indicate the existence of near-neighbor arrangements that deviate from the proposed ideal for "n-type" quenching, suggesting that charge transfer quenching is mediated by a relatively loose arrangement. © 2011 American Chemical Society. Fil:Simoncelli, S. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00027863_v133_n43_p17296_Kuzmanich
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Crystalline solids Diffusion limited Disubstituted compounds Electron-rich Excited state kinetics Femtoseconds Iodide ion Nanocrystallines Nanosecond transient absorption Orders of magnitude Parent structure Phosphorescence lifetime Quenching mechanisms Self-quenching Self-quenching effect Triplet quenching Triplet state Charge transfer Crystal structure Crystals Excited states Ion exchange Polypropylenes Rate constants Quenching 4,4' bis(dimethylamino)benzophenone 4,4' diaminobenzophenone 4,4' dihydroxybenzophenone benzophenone derivative iodide nanocrystal unclassified drug article chemical reaction kinetics chemical structure crystal structure molecular dynamics phosphorescence purification self quenching synthesis Benzophenones Kinetics Nanoparticles Oxidation-Reduction Particle Size Surface Properties
spellingShingle	Crystalline solids Diffusion limited Disubstituted compounds Electron-rich Excited state kinetics Femtoseconds Iodide ion Nanocrystallines Nanosecond transient absorption Orders of magnitude Parent structure Phosphorescence lifetime Quenching mechanisms Self-quenching Self-quenching effect Triplet quenching Triplet state Charge transfer Crystal structure Crystals Excited states Ion exchange Polypropylenes Rate constants Quenching 4,4' bis(dimethylamino)benzophenone 4,4' diaminobenzophenone 4,4' dihydroxybenzophenone benzophenone derivative iodide nanocrystal unclassified drug article chemical reaction kinetics chemical structure crystal structure molecular dynamics phosphorescence purification self quenching synthesis Benzophenones Kinetics Nanoparticles Oxidation-Reduction Particle Size Surface Properties Kuzmanich, G. Simoncelli, S. Gard, M.N. Spänig, F. Henderson, B.L. Guldi, D.M. Garcia-Garibay, M.A. Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
topic_facet	Crystalline solids Diffusion limited Disubstituted compounds Electron-rich Excited state kinetics Femtoseconds Iodide ion Nanocrystallines Nanosecond transient absorption Orders of magnitude Parent structure Phosphorescence lifetime Quenching mechanisms Self-quenching Self-quenching effect Triplet quenching Triplet state Charge transfer Crystal structure Crystals Excited states Ion exchange Polypropylenes Rate constants Quenching 4,4' bis(dimethylamino)benzophenone 4,4' diaminobenzophenone 4,4' dihydroxybenzophenone benzophenone derivative iodide nanocrystal unclassified drug article chemical reaction kinetics chemical structure crystal structure molecular dynamics phosphorescence purification self quenching synthesis Benzophenones Kinetics Nanoparticles Oxidation-Reduction Particle Size Surface Properties
description	We report an efficient triplet state self-quenching mechanism in crystals of eight benzophenones, which included the parent structure (1), six 4,4′-disubstituted compounds with NH 2 (2), NMe 2 (3), OH (4), OMe (5), COOH (6), and COOMe (7), and benzophenone-3,3′,4, 4′-tetracarboxylic dianhydride (8). Self-quenching effects were determined by measuring their triplet-triplet lifetimes and spectra using femtosecond and nanosecond transient absorption measurements with nanocrystalline suspensions. When possible, triplet lifetimes were confirmed by measuring the phosphorescence lifetimes and with the help of diffusion-limited quenching with iodide ions. We were surprised to discover that the triplet lifetimes of substituted benzophenones in crystals vary over 9 orders of magnitude from ca. 62 ps to 1 ms. In contrast to nanocrystalline suspensions, the lifetimes in solution only vary over 3 orders of magnitude (1-1000 μs). Analysis of the rate constants of quenching show that the more electron-rich benzophenones are the most efficiently deactivated such that there is an excellent correlation, ρ = -2.85, between the triplet quenching rate constants and the Hammet θ + values for the 4,4′ substituents. Several crystal structures indicate the existence of near-neighbor arrangements that deviate from the proposed ideal for "n-type" quenching, suggesting that charge transfer quenching is mediated by a relatively loose arrangement. © 2011 American Chemical Society.
format	JOUR
author	Kuzmanich, G. Simoncelli, S. Gard, M.N. Spänig, F. Henderson, B.L. Guldi, D.M. Garcia-Garibay, M.A.
author_facet	Kuzmanich, G. Simoncelli, S. Gard, M.N. Spänig, F. Henderson, B.L. Guldi, D.M. Garcia-Garibay, M.A.
author_sort	Kuzmanich, G.
title	Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
title_short	Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
title_full	Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
title_fullStr	Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
title_full_unstemmed	Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
title_sort	excited state kinetics in crystalline solids: self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism
url	http://hdl.handle.net/20.500.12110/paper_00027863_v133_n43_p17296_Kuzmanich
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Excited state kinetics in crystalline solids: Self-quenching in nanocrystals of 4,4′-disubstituted benzophenone triplets occurs by a reductive quenching mechanism

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