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The Hydrates of TEMPO: Water Vibrations Reveal Radical Microsolvation.

ABSTRACT: An organic radical monohydrate complex is detected in vacuum isolation at low temperature by FTIR supersonic jet spectroscopy for the first time. It is shown to exhibit a rich conformational and vibrational coupling dynamics, which can be drastically reduced by appropriate isotope substitution. Its detection with a new gas recycling infrared spectrometer demonstrates the thermal metastability of the gaseous TEMPO radical even under humid gas conditions. Compared to its almost isoelectronic and isostructural, closed shell ketone analogue, the hydrogen bond of the solvating water is found to be less directional, but stronger and more strongly downshifting the bonded water OH stretch vibration. A second solvent water directs the first one into a metastable hydrogen bond position to solvate the nitrogen center and the first water at the same time.

SUBMITTER: Bras EM

PROVIDER: S-EPMC8456822 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Quantum Chemical Microsolvation by Automated Water Placement.

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