New Tetrahydro‐1,2,4,5‐tetrazinan‐3‐ones and Oxoverdazyl Free Radicals.

Plater, M. John; Sinclair, James P.; Kemp, Steven; Gelbrich, Thomas; Hursthouse, Michael B.; Gómez‐García, Carlos J.

doi:10.1002/chin.200652173

Cited by 2 publications

(2 citation statements)

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“…Density-functional calculations of gas-phase molecules 6 and 7 show that the C 2 N 4 ring in 6 is planar, whereas in 7 it is nonplanar (because the C3 atom in 7 is sp 3 -hybridized), in agreement with crystallographic data. 46,47 Moreover, the phenyl group at C3 in 6 is rotated by less than 10°relative to the plane of the 6-oxoverdazyl ring, enabling extended conjugation seen in the radical's highest occupied molecular orbital (HOMO) (Figure 1). The singly occupied molecular orbital (SOMO) of 6 is clearly of π type with dominant contributions from the 2p orbitals of all four N atoms.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

et al. 2018

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The electronic structure of 1,3,5-triphenyl-6oxoverdazyl, a heteroatom-rich stable organic radical, and its diamagnetic 1,3,5-triphenyl-6-oxotetrazane precursor are probed using X-ray absorption near-edge structure (XANES) spectroscopy. The N K-edge XANES spectra of the 6-oxoverdazyl radical contain strong N 1s → π* resonances for each set of equivalent nitrogen atoms. The fact that these resonances are absent from the analogous spectra of the 6-oxotetrazane, whereas the O Kedge and C K-edge XANES spectra of both species are very similar, demonstrates that the unpaired electron of the radical is localized primarily on the N atoms of the 6-oxoverdazyl heterocycle. The O K-edge XANES spectra of both species contain strong O 1s → π* (CO) peaks, but the peak of the radical is red-shifted by 0.5 eV relative to that of the 6-oxotetrazane, which indicates that the CO bond in the radical is part of a larger π-conjugated system. The proposed interpretations of the XANES spectra are aided by density-functional calculations.

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Section: ■ Results and Discussionmentioning

confidence: 99%

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

et al. 2018

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“…[24,31] The twisting of the molecule around the N-substituents can further add to this as it is associated with a decrease in the delocalisation of the unpaired electron. [32] Based on our literature search, the electrochemistry of various verdazyl (Type I and II) molecules has been studied previously in various conventional solvents and mixtures (e.g. THF, triethylamine, acetonitrile, etc.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Properties of a Verdazyl Radical in Room Temperature Ionic Liquids

et al. 2020

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Room temperature ionic liquids (RTILs) have been widely investigated as alternative electrochemical solvents for a range of dissolved species over the past two decades. However, the behaviour of neutral radicals dissolved in RTILs is relatively unexplored. In this work, the electrochemistry of a stable verdazyl radical-1,5-dimethyl-3-phenyl-6-oxoverdazyl (MPV)has been studied on a platinum thin-film electrode using cyclic voltammetry and chronoamperometry in ten different RTILs. The organic solvent propylene carbonate is also employed as a comparison. The nature of the solvent system was found to have a large effect on the electrochemical behavior, particularly on the reduction reaction of the verdazyl radical. Chronoamperometry on a microdisk electrode was used to calculate diffusion coefficients (D's), and plots of D vs the inverse of viscosity were linear, suggesting typical hydrodynamic diffusional characteristics of the radical, in line with the behaviour of dissolved neutral and charged compounds (e.g. ferrocene and cobaltocenium) in RTILs. Overall, this study demonstrates that different RTILs have a significant influence on the electrochemistry of MPV, and therefore careful selection of the solvent system for electrochemical applications is advised.

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New Tetrahydro‐1,2,4,5‐tetrazinan‐3‐ones and Oxoverdazyl Free Radicals.

Cited by 2 publications

References 1 publication

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

X-ray Absorption Near-Edge Structure Spectroscopy of a Stable 6-Oxoverdazyl Radical and Its Diamagnetic Precursor

Electrochemical Properties of a Verdazyl Radical in Room Temperature Ionic Liquids

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