Structural Dynamics of C2F4I2 in Cyclohexane Studied via Time-Resolved X-ray Liquidography

The halogen elimination of 1,2-diiodoethane (C2H4I2) and 1,2-diiodotetrafluoroethane (C2F4I2) serves as a model reaction for investigating the influence of fluorination on reaction dynamics and solute-solvent interactions in solution-phase reactions. While the kinetics and reaction pathways of the halogen elimination reaction of C2H4I2 were reported to vary substantially depending on the solvent, the solvent effects on the photodissociation of C2F4I2 remain to be explored, as its reaction dynamics have only been studied in methanol. Here, to investigate the solvent dependence, we conducted a time-resolved X-ray liquidography (TRXL) experiment on C2F4I2 in cyclohexane. The data revealed that (i) the solvent dependence of the photoreaction of C2F4I2 is not as strong as that observed for C2H4I2, and (ii) the nongeminate recombination leading to the formation of I-2 is slower in cyclohexane than in methanol. We also show that the molecular structures of the relevant species determined from the structural analysis of TRXL data provide an excellent benchmark for DFT calculations, especially for investigating the relevance of exchange-correlation functionals used for the structural optimization of haloalkanes. This study demonstrates that TRXL is a powerful technique to study solvent dependence in the solution phase.

Automated summary

The study investigated the influence of fluorination on the reaction dynamics and solute-solvent interactions in solution-phase reactions by conducting a TRXL experiment on C2F4I2 in cyclohexane. The data revealed that the solvent dependence of C2F4I2's photoreaction is less significant than that of C2H4I2, and the nongeminate recombination leading to the formation of I-2 is slower in cyclohexane compared to methanol.