Latent photochromism (pseudothermochromism) and photofatigue of crystalline 2-(2′,4′-dinitrobenzyl)pyridine

Pance Naumov, Yuji Ohashi

Research output: Contribution to journalArticle

Abstract

Along with the metastable 2-(2′,4′-dinitrophenylmethylidene)-1,2-dihydropyridine (NH) and the unstable 6-aci-nitro-2-nitro-5-(2′-pyridylmethylene)-1,3-cyclohexadiene (OH), the stable form of 2-(2′,4′-dinitrobenzyl)pyridine (DNBP), CH, is photochemically converted into small amounts of 1,2-bis(2′,4′-dinitrophenyl)-1,2-bis(2′-pyridyl)ethane, trans-bis[5-nitro-2-(pyridine-2-carbonyl)phenyl]diazene N-oxide, 6-nitro-3-(2′-pyridyl)-2,1-benzisoxazole and 3-nitropyrido[1,2-b]quinolin-6-ium-11-olate. The latent photochromism of DNBP, as shown by x-ray analysis of the structures of the side-products and ESR/IR measurements, is attributed to open-shell reactions that are initiated by hydrogen photoabstraction and subsequent creation of two monoradicals, NH ̇ and OḢ. Large amounts of the radicals (ca 50% NḢ and 70% OḢ) confined in the crystalline interior are persistent under ambient conditions. Through quasi-periodic reactions, the remaining radicals partially recover the ground-state isomers CH, NH and OH, or decay to the side-products, which results in crystalline photofatigue. Together with proton tunneling from the excited CH, the radical reactions represent dominant mechanism for the creation of NH and OH in the low-temperature regimes, but are successfully competed by the closed-shell reactions at higher temperatures. The precursor state, whose existence was assumed previously from transient absorption spectroscopy, may be identified as the radical OḢ. The present work represents the first study of the photofatigue of a 2-(2′,4′-dinitrobenzyl)pyridine compound and extends the 'classical' mechanism of the photochromic reactions of nitrobenzylpyridines with a set of open-shell radical reaction routes.

Original languageEnglish (US)
Pages (from-to)865-875
Number of pages11
JournalJournal of Physical Organic Chemistry
Volume17
Issue number10
DOIs
StatePublished - Oct 1 2004

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Photochromism
photochromism
pyridines
Crystalline materials
methylidyne
Ethane
Absorption spectroscopy
Isomers
Oxides
Ground state
Paramagnetic resonance
Protons
Hydrogen
x ray analysis
quinoline
products
X rays
ethane
Temperature
pyridine

Keywords

  • 2-(2′,4′-Dinitrobenzyl)pyridine
  • Nitrobenzylpyridines
  • Photochromic ortho-nitrobenzylpyridine
  • Photochromism
  • Photofatigue
  • Radicals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Latent photochromism (pseudothermochromism) and photofatigue of crystalline 2-(2′,4′-dinitrobenzyl)pyridine. / Naumov, Pance; Ohashi, Yuji.

In: Journal of Physical Organic Chemistry, Vol. 17, No. 10, 01.10.2004, p. 865-875.

Research output: Contribution to journalArticle

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abstract = "Along with the metastable 2-(2′,4′-dinitrophenylmethylidene)-1,2-dihydropyridine (NH) and the unstable 6-aci-nitro-2-nitro-5-(2′-pyridylmethylene)-1,3-cyclohexadiene (OH), the stable form of 2-(2′,4′-dinitrobenzyl)pyridine (DNBP), CH, is photochemically converted into small amounts of 1,2-bis(2′,4′-dinitrophenyl)-1,2-bis(2′-pyridyl)ethane, trans-bis[5-nitro-2-(pyridine-2-carbonyl)phenyl]diazene N-oxide, 6-nitro-3-(2′-pyridyl)-2,1-benzisoxazole and 3-nitropyrido[1,2-b]quinolin-6-ium-11-olate. The latent photochromism of DNBP, as shown by x-ray analysis of the structures of the side-products and ESR/IR measurements, is attributed to open-shell reactions that are initiated by hydrogen photoabstraction and subsequent creation of two monoradicals, NH ̇ and OḢ. Large amounts of the radicals (ca 50{\%} NḢ and 70{\%} OḢ) confined in the crystalline interior are persistent under ambient conditions. Through quasi-periodic reactions, the remaining radicals partially recover the ground-state isomers CH, NH and OH, or decay to the side-products, which results in crystalline photofatigue. Together with proton tunneling from the excited CH, the radical reactions represent dominant mechanism for the creation of NH and OH in the low-temperature regimes, but are successfully competed by the closed-shell reactions at higher temperatures. The precursor state, whose existence was assumed previously from transient absorption spectroscopy, may be identified as the radical OḢ. The present work represents the first study of the photofatigue of a 2-(2′,4′-dinitrobenzyl)pyridine compound and extends the 'classical' mechanism of the photochromic reactions of nitrobenzylpyridines with a set of open-shell radical reaction routes.",
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N2 - Along with the metastable 2-(2′,4′-dinitrophenylmethylidene)-1,2-dihydropyridine (NH) and the unstable 6-aci-nitro-2-nitro-5-(2′-pyridylmethylene)-1,3-cyclohexadiene (OH), the stable form of 2-(2′,4′-dinitrobenzyl)pyridine (DNBP), CH, is photochemically converted into small amounts of 1,2-bis(2′,4′-dinitrophenyl)-1,2-bis(2′-pyridyl)ethane, trans-bis[5-nitro-2-(pyridine-2-carbonyl)phenyl]diazene N-oxide, 6-nitro-3-(2′-pyridyl)-2,1-benzisoxazole and 3-nitropyrido[1,2-b]quinolin-6-ium-11-olate. The latent photochromism of DNBP, as shown by x-ray analysis of the structures of the side-products and ESR/IR measurements, is attributed to open-shell reactions that are initiated by hydrogen photoabstraction and subsequent creation of two monoradicals, NH ̇ and OḢ. Large amounts of the radicals (ca 50% NḢ and 70% OḢ) confined in the crystalline interior are persistent under ambient conditions. Through quasi-periodic reactions, the remaining radicals partially recover the ground-state isomers CH, NH and OH, or decay to the side-products, which results in crystalline photofatigue. Together with proton tunneling from the excited CH, the radical reactions represent dominant mechanism for the creation of NH and OH in the low-temperature regimes, but are successfully competed by the closed-shell reactions at higher temperatures. The precursor state, whose existence was assumed previously from transient absorption spectroscopy, may be identified as the radical OḢ. The present work represents the first study of the photofatigue of a 2-(2′,4′-dinitrobenzyl)pyridine compound and extends the 'classical' mechanism of the photochromic reactions of nitrobenzylpyridines with a set of open-shell radical reaction routes.

AB - Along with the metastable 2-(2′,4′-dinitrophenylmethylidene)-1,2-dihydropyridine (NH) and the unstable 6-aci-nitro-2-nitro-5-(2′-pyridylmethylene)-1,3-cyclohexadiene (OH), the stable form of 2-(2′,4′-dinitrobenzyl)pyridine (DNBP), CH, is photochemically converted into small amounts of 1,2-bis(2′,4′-dinitrophenyl)-1,2-bis(2′-pyridyl)ethane, trans-bis[5-nitro-2-(pyridine-2-carbonyl)phenyl]diazene N-oxide, 6-nitro-3-(2′-pyridyl)-2,1-benzisoxazole and 3-nitropyrido[1,2-b]quinolin-6-ium-11-olate. The latent photochromism of DNBP, as shown by x-ray analysis of the structures of the side-products and ESR/IR measurements, is attributed to open-shell reactions that are initiated by hydrogen photoabstraction and subsequent creation of two monoradicals, NH ̇ and OḢ. Large amounts of the radicals (ca 50% NḢ and 70% OḢ) confined in the crystalline interior are persistent under ambient conditions. Through quasi-periodic reactions, the remaining radicals partially recover the ground-state isomers CH, NH and OH, or decay to the side-products, which results in crystalline photofatigue. Together with proton tunneling from the excited CH, the radical reactions represent dominant mechanism for the creation of NH and OH in the low-temperature regimes, but are successfully competed by the closed-shell reactions at higher temperatures. The precursor state, whose existence was assumed previously from transient absorption spectroscopy, may be identified as the radical OḢ. The present work represents the first study of the photofatigue of a 2-(2′,4′-dinitrobenzyl)pyridine compound and extends the 'classical' mechanism of the photochromic reactions of nitrobenzylpyridines with a set of open-shell radical reaction routes.

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