ArticleAngewandte Chemie (International ed. in English)2024
Fast Collective Hydrogen-Bond Dynamics in Hexafluoroisopropanol Related to its Chemical Activity.
Article in Angewandte Chemie (International ed. in English), 2024. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 6 papers.
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Who cites it
6 citing papers in PubMed.
- Stable P-Type PbS Quantum Dot Ink for all-Blade-Coated Short-Wavelength Infrared Photodiodes.Advanced materials (Deerfield Beach, Fla.) · 2026Article
- Synthesis of Unsymmetrical Dialkyl Ethers via Direct Etherification Cocatalyzed Using FeClACS omega · 2026Article
- EDA Complex-Driven Desaturation of Heterocyclic Carbonyl Compounds Enabled by HFIP.Angewandte Chemie (International ed. in English) · 2025Article
- Triarylpyrylium-based fluorescent DNA-binding dyes - facile synthesis, substituent effects, and sensing mechanism.RSC advances · 2025Article
- Room-Temperature Material Recycling/Upcycling of Polyamide Waste Enabled by Cosolvent-Tunable Dissolution Kinetics.Angewandte Chemie (International ed. in English) · 2025Article
- Fast Collective Hydrogen-Bond Dynamics in Hexafluoroisopropanol Related to its Chemical Activity.Angewandte Chemie (International ed. in English) · 2024Article
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Authors and funding
5 authors.
Funding
Abstract
Using fluorinated mono-alcohols, in particular hexafluoro-isopropanol (HFIP), as a solvent can enhance chemical reaction rates in a spectacular manner. Previous work has shown evidence that this enhancement is related to the hydrogen-bond structure of these liquids. Here, we investigate the hydrogen-bond dynamics of HFIP and compare it to that of its non-fluorinated analog, isopropanol. Ultrafast infrared spectroscopy experiments show that the dynamics of individual hydrogen-bonds is about twice as slow in HFIP as in isopropanol. Surprisingly, from dielectric spectroscopy we find the opposite behavior for the dynamics of hydrogen-bonded clusters: collective rearrangements are 3 times faster in HFIP than in isopropanol. This difference indicates that the hydrogen-bonded clusters in HFIP are smaller than in isopropanol. The differences in cluster size can be traced to changes in the hydrogen-bond donor and acceptor strengths upon fluorination. The smaller cluster size can boost reaction rates in HFIP by increasing the concentration of reactive, terminal OH-groups of the clusters, whereas the fast collective dynamics can increase the rate of formation of hydrogen-bonds with the reactants. The longer lifetime of the individual hydrogen-bonds in HFIP can enhance the stability of the hydrogen-bonded clusters, and so increase the probability of reactant-solvent hydrogen-bonding.
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