Anionic Dimers of Fluorinated Alcohols.

Area of Science:

• Physical Chemistry
• Supramolecular Chemistry
• Fluorine Chemistry

Background:

• Fluorinated alcohols exhibit unique properties due to fluorine's electronegativity.
• Understanding their self-association is crucial for applications in various chemical processes.
• Anionic species play a significant role in the solution behavior of alcohols.

Purpose of the Study:

• To investigate the formation and stability of anionic dimers of fluorinated alcohols.
• To determine the kinetic and thermodynamic parameters governing the exchange reactions of these dimers.
• To elucidate the influence of fluorination degree on alcohol association.

Main Methods:

• Negative-ion mode electrospray ionization mass spectrometry
• Quadrupole-ion trap experiments for kinetic data acquisition
• Quantum chemical calculations for structural and energetic analysis

Main Results:

• Anionic dimers of the type (RO)2H- and (RO)(RO)H- were identified for ethanol and its fluorinated analogs.
• Exchange reactions revealed that dimer formation is favored for more highly fluorinated alcohols.
• Quantum chemical calculations confirmed this trend and provided dissociation energies, showing increased stability with higher fluorination.

Conclusions:

• The stability of anionic dimers increases with the degree of alcohol fluorination.
• Enhanced hydrogen-bond donor ability of fluorinated alcohols contributes to stronger dimer interactions.
• These findings enhance the understanding of molecular interactions and association in fluorinated alcohol solutions.