Radical species derived from phenalenone: Characterization and role of upper excited states

Cristina Flors; Santi Nonell

doi:10.1016/j.jphotochem.2004.01.001

Radical species derived from phenalenone: Characterization and role of upper excited states

Cristina Flors
, Santi Nonell^*

^*Autor/a de correspondencia de este trabajo

Producción científica: Artículo en revista indizada › Artículo › revisión exhaustiva

20 Citas (Scopus)

Resumen

The reactivity of triplet phenalenone (PN) towards typical H- and electron-donors is characterized by means of nanosecond laser flash-photolysis. H-abstraction from tributylstannane occurs with a rate constant of ca. 5×10⁵ M^-1 s^-1. From the activation energy for this reaction, an upper limit for the T₂-T₁ energy gap is calculated as 9±1 kJ mol^-1 in nonpolar solvents, consistent with the solvent-insensitive high Φ_T value in phenalenone. Triplet phenalenone also reacts via photoinduced electron transfer with 1,4-diazabicyclo[2.2.2]octane (DABCO) with rate constant close to the diffusional control limit. The spectrum of the solvated free radical anion of phenalenone has a maximum at 440 nm in acetonitrile.

Idioma original	Inglés
Páginas (desde-hasta)	9-12
Número de páginas	4
Publicación	Journal of Photochemistry and Photobiology A: Chemistry
Volumen	163
N.º	1-2
DOI	https://doi.org/10.1016/j.jphotochem.2004.01.001
Estado	Publicada - 15 abr 2004

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@article{988852b92b4a4ac186abece2e1a8c70c,

title = "Radical species derived from phenalenone: Characterization and role of upper excited states",

abstract = "The reactivity of triplet phenalenone (PN) towards typical H- and electron-donors is characterized by means of nanosecond laser flash-photolysis. H-abstraction from tributylstannane occurs with a rate constant of ca. 5×105 M-1 s-1. From the activation energy for this reaction, an upper limit for the T2-T1 energy gap is calculated as 9±1 kJ mol-1 in nonpolar solvents, consistent with the solvent-insensitive high ΦT value in phenalenone. Triplet phenalenone also reacts via photoinduced electron transfer with 1,4-diazabicyclo[2.2.2]octane (DABCO) with rate constant close to the diffusional control limit. The spectrum of the solvated free radical anion of phenalenone has a maximum at 440 nm in acetonitrile.",

keywords = "Aromatic ketone, Hydrogen abstraction, Ketyl radical, Phenalenone, Photoinduced electron transfer, Radical anion",

author = "Cristina Flors and Santi Nonell",

year = "2004",

month = apr,

day = "15",

doi = "10.1016/j.jphotochem.2004.01.001",

language = "English",

volume = "163",

pages = "9--12",

journal = "Journal of Photochemistry and Photobiology A: Chemistry",

issn = "1010-6030",

publisher = "Elsevier B.V.",

number = "1-2",

}

TY - JOUR

T1 - Radical species derived from phenalenone

T2 - Characterization and role of upper excited states

AU - Flors, Cristina

AU - Nonell, Santi

PY - 2004/4/15

Y1 - 2004/4/15

N2 - The reactivity of triplet phenalenone (PN) towards typical H- and electron-donors is characterized by means of nanosecond laser flash-photolysis. H-abstraction from tributylstannane occurs with a rate constant of ca. 5×105 M-1 s-1. From the activation energy for this reaction, an upper limit for the T2-T1 energy gap is calculated as 9±1 kJ mol-1 in nonpolar solvents, consistent with the solvent-insensitive high ΦT value in phenalenone. Triplet phenalenone also reacts via photoinduced electron transfer with 1,4-diazabicyclo[2.2.2]octane (DABCO) with rate constant close to the diffusional control limit. The spectrum of the solvated free radical anion of phenalenone has a maximum at 440 nm in acetonitrile.

AB - The reactivity of triplet phenalenone (PN) towards typical H- and electron-donors is characterized by means of nanosecond laser flash-photolysis. H-abstraction from tributylstannane occurs with a rate constant of ca. 5×105 M-1 s-1. From the activation energy for this reaction, an upper limit for the T2-T1 energy gap is calculated as 9±1 kJ mol-1 in nonpolar solvents, consistent with the solvent-insensitive high ΦT value in phenalenone. Triplet phenalenone also reacts via photoinduced electron transfer with 1,4-diazabicyclo[2.2.2]octane (DABCO) with rate constant close to the diffusional control limit. The spectrum of the solvated free radical anion of phenalenone has a maximum at 440 nm in acetonitrile.

KW - Aromatic ketone

KW - Hydrogen abstraction

KW - Ketyl radical

KW - Phenalenone

KW - Photoinduced electron transfer

KW - Radical anion

UR - https://www.scopus.com/pages/publications/1342264913

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U2 - 10.1016/j.jphotochem.2004.01.001

DO - 10.1016/j.jphotochem.2004.01.001

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VL - 163

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JO - Journal of Photochemistry and Photobiology A: Chemistry

JF - Journal of Photochemistry and Photobiology A: Chemistry

IS - 1-2

ER -

Radical species derived from phenalenone: Characterization and role of upper excited states

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