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Sensing the ortho Positions in C6Cl6 and C6H4Cl2 from Cl2− Formation upon Molecular Reduction
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Resumo(s)
The geometrical effect of chlorine atom positions in polyatomic molecules after capturing a low-energy electron is shown to be a prevalent mechanism yielding Cl2−. In this work, we investigated hexachlorobenzene reduction in electron transfer experiments to determine the role of chlorine atom positions around the aromatic ring, and compared our results with those using ortho-, meta- and para-dichlorobenzene molecules. This was achieved by combining gas-phase experiments to determine the reaction threshold by means of mass spectrometry together with quantum chemical calculations. We also observed that Cl2− formation can only occur in 1,2-C6H4Cl2, where the two closest C–Cl bonds are cleaved while the chlorine atoms are brought together within the ring framework due to excess energy dissipation. These results show that a strong coupling between electronic and C–Cl bending motion is responsible for a positional isomeric effect, where molecular recognition is a determining factor in chlorine anion formation.
Descrição
This work was also supported by Radiation Biology and Biophysics Doctoral Training Programme (RaBBiT, PD/00193/2012).
GG acknowledges partial financial support from the Spanish Ministerio de Ciencia e Innovación (Project No. PID2019-104727RBC21), Ministerio de Universidades (Project No. PRX21-00340) and CSIC (Project LINKA20085). The work is part of COST Action CA18212—Molecular Dynamics in the GAS phase (MD-GAS).
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© 2022 by the authors.
Palavras-chave
charge transfer collision induced dissociation dichlorobenzene geometric effect hexachlorobenzene Analytical Chemistry Chemistry (miscellaneous) Molecular Medicine Pharmaceutical Science Drug Discovery Physical and Theoretical Chemistry Organic Chemistry