Photochemical decomposition of 2,4,6-trinitrotoluene and related compounds in ethers

Davis, Larry P.; Wilkes, John S.; Pugh, Henry L.; Dorey, R. Cameron

doi:10.1021/j150623a028

Cited by 19 publications

(1 citation statement)

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“…Herein, we report the rather unexpected photochemical generation of radicals in an aluminum-based MOF, in which the source of reactivity is the linker molecule 5-nitroisophthalic acid. Although nitro-aromatics were shown to be photochemically active and to form anionic radicals, , 5-nitroisophthalate has not been described yet as a photoreactive building block.…”

Section: Introductionmentioning

confidence: 99%

Unexpected Photoreactivity in a NO₂-Functionalized Aluminum-MOF

et al. 2015

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The metal–organic framework CAU-10-NO2 [Al(OH)BDC-NO2] (CAU stands for Christian-Albrechts-University; H2BDC-NO2 is 5-nitroisophthalic acid) was observed to exhibit unexpected photochemical reactivity. Upon irradiation of the MOF with UV light with a wavelength of 365 nm (or with sunlight), guest molecules inside the pore system of the MOF can be oxidized and stable radicals are formed from the organic linker molecules. The reactivity toward different alcohols was studied by UV/vis spectroscopy and EPR spectroscopy. The amount of generated radicals depends on the size of the solvent molecules; however, as an exception, methanol shows a much lower reactivity than ethanol. DFT calculations were carried out to gain insights into these photochemical reactions. The results indicate that the nitro group is reduced to form a nitroso moiety. This was confirmed by means of NMR spectroscopy. The exact nature of the radical could not be revealed, but the results indicate that it could be a further reduced anionic nitroso radical. Methanol and ethanol can be distinguished using this photochemical reaction simply by the coloring of the irradiated MOF. Such a property is characteristic for a sensor; therefore, a synthesis procedure was developed to implement the MOF into a device by which the compound was directly grown onto gold substrates.

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Section: Introductionmentioning

confidence: 99%

Unexpected Photoreactivity in a NO₂-Functionalized Aluminum-MOF

et al. 2015

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ChemInform Abstract: PHOTOCHEMICAL DECOMPOSITION OF 2,4,6‐TRINITROTOLUENE AND RELATED COMPOUNDS IN ETHERS

Davis¹,

Wilkes²,

Pugh³

et al. 1982

Chemischer Informationsdienst

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An EPR study of the thermal decomposition of molten 2,4,6‐trinitrotoluene and its isotopic analogs

Swanson

Davis

Dorey

et al. 1986

Magnetic Reson in Chemistry

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Electron paramagnetic resonance spectroscopy has been used to probe the decomposition pathway of neat molten 2,4,6-trinitrotoiuene (TNT). The analogs of TNT labelled in the 2-, 2,6-, 4-and 2,4,6positions with =N, and labelled in the it-, 3,s-and a,3,5-position with *H have been studied, and their spectra recorded at 240 "C. The results indicate that the earliest observable radical produces a spectrum resulting from coupling with a para-N (aN=10.8G), five equivalent hydrogens (aH=2.7G) and two benzylic hydrogens (aH= 10.7 G):

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Photochemical decomposition of 2,4,6-trinitrotoluene and related compounds in ethers

Cited by 19 publications

References 13 publications

Unexpected Photoreactivity in a NO₂-Functionalized Aluminum-MOF

Unexpected Photoreactivity in a NO₂-Functionalized Aluminum-MOF

ChemInform Abstract: PHOTOCHEMICAL DECOMPOSITION OF 2,4,6‐TRINITROTOLUENE AND RELATED COMPOUNDS IN ETHERS

An EPR study of the thermal decomposition of molten 2,4,6‐trinitrotoluene and its isotopic analogs

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Photochemical decomposition of 2,4,6-trinitrotoluene and related compounds in ethers

Cited by 19 publications

References 13 publications

Unexpected Photoreactivity in a NO2-Functionalized Aluminum-MOF

Unexpected Photoreactivity in a NO2-Functionalized Aluminum-MOF

ChemInform Abstract: PHOTOCHEMICAL DECOMPOSITION OF 2,4,6‐TRINITROTOLUENE AND RELATED COMPOUNDS IN ETHERS

An EPR study of the thermal decomposition of molten 2,4,6‐trinitrotoluene and its isotopic analogs

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Unexpected Photoreactivity in a NO₂-Functionalized Aluminum-MOF

Unexpected Photoreactivity in a NO₂-Functionalized Aluminum-MOF