Photochemical transformations of pyridinium salts: mechanistic studies and applications in synthesis

Damiano, Teresa; Morton, Daniel; Nelson, Adam

doi:10.1039/b706244n

Cited by 59 publications

(37 citation statements)

References 71 publications

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“…17,[23][24][25] This behaviour is a familiar feature in the deactivation of electronically excited aromatics and has been observed experimentally for pyridine. 17,23,26,27 While control over this transformation may have promising synthetic applications, 28 it presents a significant spectroscopic challenge. The N -pyridinium ion photodissociates to form the 2-pyridinylium ion and molecular hydrogen following ultraviolet excitation in the region 37 000 -45 000 cm −1 (270 -220 nm).…”

Section: 15mentioning

confidence: 99%

Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

Hansen

Blanksby

Chalyavi

et al. 2015

The Journal of Chemical Physics

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The S1←S0 electronic transition of the N-pyridinium ion (C5H5NH+) is investigated using ultraviolet photodissociation (PD) spectroscopy of the bare ion and also the N2-tagged complex. Gas-phase Npyridinium ions photodissociate by the loss of molecular hydrogen (H2) in the photon energy range 37 000-45 000 cm−1 with structurally diagnostic ion-molecule reactions identifying the 2-pyridinylium ion as the exclusive co-product. The photodissociation action spectra reveal vibronic details that, with the aid of electronic structure calculations, support the proposal that dissociation occurs through an intramolecular rearrangement on the ground electronic state following internal conversion. Quantum chemical calculations are used to analyze the measured spectra. Most of the vibronic features are attributed to progressions of totally symmetric ring deformation modes and out-of-plane modes active in the isomerization of the planar excited state towards the non-planar excited state global minimum. The S 1 ← S 0 electronic transition of the N -pyridinium ion (C 5 H 5 NH + ) is investigated using ultraviolet photodissociation spectroscopy of the bare ion and also the N 2 -tagged complex. Gas-phase N -pyridinium ions photodissociate by the loss of molecular hydrogen (H 2 ) in the photon energy range 37 000 -45 000 cm

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Section: 15mentioning

confidence: 99%

Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

Hansen

Blanksby

Chalyavi

et al. 2015

The Journal of Chemical Physics

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“…Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Damiano et al, 2007). As part of our ongoing studies of supramolecular chemistry involving the pyridinium rings , an Xray structure analysis of the title compound has been performed.…”

Section: Methodsmentioning

confidence: 99%

“…For non-conventional hydrogen bonds, see: Desiraju & Steiner (2001). For the use of pyridinium derivatives in the construction of supramolecular architectures, see: Damiano et al (2007).…”

Section: Related Literaturementioning

confidence: 99%

4-(4-Nitrobenzenesulfonamido)pyridinium bromide

Zhao

Yu²,

2008

Acta Cryst E

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“…Damiano et al (2007) describe the use of pyridinium derivatives for the construction of supramolecular architectures. For bond-length data, see: Allen et al (1987).…”

Section: Related Literaturementioning

confidence: 99%

“…Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Damiano et al, 2007). As part of our ongoing studies of supramolecular chemistry involving the pyridinium rings , the structure of the title compound was determined by X-ray diffraction.…”

Section: S1 Commentmentioning

confidence: 99%

4-(2-Nitrobenzenesulfonamido)pyridinium nitrate

Zhao

2008

Acta Cryst E

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Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Damiano et al., 2007). As part of our ongoing studies of supramolecular chemistry involving the pyridinium rings (Li et al., 2007), the structure of the title compound was determined by X-ray diffraction. In the cations of the title compound the short C-N distance [N2-C1 = 1.389 (3)Å and N5-C12 = 1.382 (3)Å] has a value between those of a typical C═N double and C-N single bond (1.47-1.50Å and 1.34-1.38Å, respectively; Allen et al., 1987). This might be indicative of a slight conjugation of the N sulfonamide π-electrons with those of the pyridinium ring. In the two symmetry-independent molecules (Fig. 1), the dihedral angles between the benzene ring and the pyridinium ring are 85.1 (1)° and 86.2 (1)° respectively. The dihedral angles between the nitro-group and the benzene ring are 41.2 (1)° and 40.5 (2)° respectively. S2. Experimental A solution of 2-nitrobenzenesulfonyl chloride (2.2 g, 10 mmol) in CH 2 Cl 2 (10 ml) was added dropwise to a suspension of 4-aminopyridine (0.9 g, 10 mmol) in CH 2 Cl 2 (10 ml) at room temperature with stirring. The reaction mixture was stirred overnight. The yellow solid obtained was washed with warm water to obtain the title compound in a yield of 52.9%. A colourless single crystals, suitable for X-ray analysis were obtained by slow evaporation of an nitric acid (10%) solution at room temperature over a period of a week. S3. Refinement The N-bound H atoms were located in a difference map and refined isotropically. The C-bound H atoms were positioned geometrically (C-H = 0.95 Å) and refined as riding with U iso (H) = 1.2U eq (C). supporting information sup-2 Acta Cryst. (2008). E64, o2281 supporting information sup-7

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Photochemical transformations of pyridinium salts: mechanistic studies and applications in synthesis

Cited by 59 publications

References 71 publications

Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

Ultraviolet photodissociation action spectroscopy of the N-pyridinium cation

4-(4-Nitrobenzenesulfonamido)pyridinium bromide

4-(2-Nitrobenzenesulfonamido)pyridinium nitrate

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