IR induced photochemistry of glycolaldehyde in nitrogen matrix

Duvernay, Fabrice; Butscher, Teddy; Chiavassa, Thierry; Coussan, S.

doi:10.1016/j.chemphys.2017.08.010

Cited by 6 publications

(3 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is the first report of such a conformational conversion occurring in an amide molecule. Hitherto, near-IR-induced conformational conversions occurring by torsion of molecular fragments around the C–C bond have been reported for several compounds: hydroxyacetone, glycine, glycolaldehyde, glycolic acid, kojic acid, and propionic acid . These experimental results, together with those obtained in the current work for glycolamide, provide convincing evidence demonstrating that near-IR excitation of 2νOH or 2νNH 2 overtones of OH or NH 2 groups attached in an α position may lead to conformational transformation involving torsion of fragments around the central single C–C bond.…”

Section: Concluding Discussionmentioning

confidence: 99%

Conformational Isomerizations by Rotation around C–C or C–N Bonds: A Comparative Study on Matrix-Isolated Glycolamide and N-Hydroxyurea Excited with Near-IR Laser Light

et al. 2019

View full text Add to dashboard Cite

Conformers and near-IR-induced conformational transformations were studied for monomers of glycolamide isolated in low-temperature matrixes. Two conformational isomers of the compound, Tt and Cc, were trapped from the gas phase into solid Ar matrixes. Selective near-IR excitation of glycolamide molecules adopting the Tt form led to the Tt → Cc conformational conversion. Analogously, selective near-IR excitation of Cc conformers resulted in the Cc → Tt transformation. Monochromatic near-IR light, generated by frequency-tunable laser sources, was used for irradiation of matrix-isolated monomers. Near-IR-induced Tt → Cc and Cc → Tt conformational transformations occurred upon excitation of 2νOH, 2ν a NH 2 , and 2ν s NH 2 overtones, as well as upon excitation of ν a NH 2 + ν s NH 2 combination modes. In spite of the structural similarity of glycolamide and N-hydroxyurea, no conformational conversions were observed for monomers of the latter compound isolated in Ar matrixes and excited with near-IR light. The comparison of the effects of near-IR excitations of glycolamide and N-hydroxyurea demonstrates that transformations involving rotation of molecular fragments around a single C−C bond occur much easier than transformations involving rotation of the fragments around a C−N bond. The efficiency of the latter conversions is extremely low.

show abstract

Section: Concluding Discussionmentioning

confidence: 99%

Conformational Isomerizations by Rotation around C–C or C–N Bonds: A Comparative Study on Matrix-Isolated Glycolamide and N-Hydroxyurea Excited with Near-IR Laser Light

et al. 2019

View full text Add to dashboard Cite

show abstract

“…This way, conformational changes overcoming a torsional barrier up to almost 60 kJ mol À1 have been achieved. 10 Vibrational excitations of fundamental modes like OH, NH and CH stretching (or modes with a similar energy, B45-30 kJ mol À1 ) have also been applied to induce rotamerization, [24][25][26] but such cases are inherently constrained to lower torsional barriers and lower quantum yields. 7 To the best of our knowledge, vibrational excitation of a second stretching overtone (up to 130-120 kJ mol À1 ) has never been considered before in this context.…”

Section: Introductionmentioning

confidence: 99%

Conformational isomerizations triggered by vibrational excitation of second stretching overtones

Nunes

Reva

Fausto

2019

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…One noticeable exception has been the use of vibrational excitation to manipulate molecular conformations of different classes of organic compounds. − In general, such transformations are explored with help of the low-temperature matrix isolation technique, which provides ideal conditions for investigating chemical processes with low energy barriers, suitable to be activated by IR light . Typically, energy is deposited in XH (X = O or N) first stretching overtones, because these modes have substantial energy alongside with a sufficiently significant absorption cross section .…”

mentioning

confidence: 99%

Bond-Breaking/Bond-Forming Reactions by Vibrational Excitation: Infrared-Induced Bidirectional Tautomerization of Matrix-Isolated Thiotropolone

Nunes

Pereira

Reva

et al. 2020

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Infrared vibrational excitation is a promising approach for gaining exceptional control of chemical reactions, in ways that cannot be attained via thermal or electronic excitation. Here, we report an unprecedented example of a bond-breaking/bond-forming reaction by vibrational excitation under matrix isolation conditions. Thiotropolone monomers were isolated in cryogenic argon matrices and characterized by infrared spectroscopy and vibrational computations (harmonic and anharmonic). Narrowband near-infrared irradiations tuned at frequencies of first CH stretching overtone (5940 cm–1) or combination modes (5980 cm–1) of the OH tautomer, the sole form of the compound that exists in the as-deposited matrices, led to its conversion into the SH tautomer. The tautomerization in the reverse direction was achieved by vibrational excitation of the SH tautomer with irradiation at 5947 or 5994 cm–1, corresponding to the frequencies of its CH stretching combination and overtone modes. This pioneer demonstration of bidirectional hydroxyl ↔ thiol tautomerization controlled by vibrational excitation creates prospects for new advances in vibrationally induced chemistry.

show abstract

IR induced photochemistry of glycolaldehyde in nitrogen matrix

Cited by 6 publications

References 39 publications

Conformational Isomerizations by Rotation around C–C or C–N Bonds: A Comparative Study on Matrix-Isolated Glycolamide and N-Hydroxyurea Excited with Near-IR Laser Light

Conformational Isomerizations by Rotation around C–C or C–N Bonds: A Comparative Study on Matrix-Isolated Glycolamide and N-Hydroxyurea Excited with Near-IR Laser Light

Conformational isomerizations triggered by vibrational excitation of second stretching overtones

Bond-Breaking/Bond-Forming Reactions by Vibrational Excitation: Infrared-Induced Bidirectional Tautomerization of Matrix-Isolated Thiotropolone

Contact Info

Product

Resources

About