Mass Spectrometry Evidence for Self-Rigidification of π-Conjugated Oligomers Containing 3,4-Ethylenedioxythiophene (EDOT) Groups using RRKM Theory and Internal Energy Calibration

David Rondeau (1) , Yves Gimbert (2) , Karoly Vekey (3) , Laszlo Drahos (4) , Mathieu Turbiez (5) , Pierre Frère (5) , Jean Roncali (6)

1 IETR - Institut d'Électronique et des Technologies du numéRique
2 DCM - SeRCO - Département de Chimie Moléculaire - Synthèse Et Réactivité en Chimie Organique
3 HAS CRC - Hungarian Academy of Sciences, Chemical Research Center
4 MTA - Hungarian Academy of Sciences
5 MOLTECH-Anjou
6 CIMMA - Chimie, Ingénierie Moléculaire et Matériaux d'Angers

The self-rigidification of ionized π-conjugated systems based on two combinations of thiophene (T) and 3,4-Ethylenedioxythiophene (E) is investigated using mass-analyzed ion kinetic energy spectrometry (MIKES) of ions produced from electron impact ionization at 70 eV. The m/z 446 radical cations of the two isomers ETTE and TEET lead to detect m/z 418 and 390 daughter ions. The MIKE spectra differ only by the intensities of these fragment ions. As the m/z 418 daughter ion is produced through a same retro-Diels Alder reaction whatever

Mots clés: Conjugated systems; MIKES; RRKM; oligothiophenes; unimolecular dissociations

Domaines: Chimie analytique

David Rondeau, Yves Gimbert, Karoly Vekey, Laszlo Drahos, Mathieu Turbiez, et al.. Mass Spectrometry Evidence for Self-Rigidification of π-Conjugated Oligomers Containing 3,4-Ethylenedioxythiophene (EDOT) Groups using RRKM Theory and Internal Energy Calibration. European Journal of Mass Spectrometry, 2019, 25 (2), pp.239-250. ⟨10.1177/1469066718811712⟩. ⟨hal-02616097⟩