AI Article Synopsis
- The study investigates how adding fluorine affects the hydrogen-bonding ability and conformation of benzyl alcohols using both experimental (IR spectroscopy) and theoretical methods (quantum chemistry).
- It was found that introducing a single fluorine atom increases the hydrogen-bond acidity of the hydroxyl group, while adding two fluorine atoms decreases it.
- The presence of fluorine significantly influences the compounds' conformations and interactions, with specific intramolecular forces (like OH⋅⋅⋅F) playing a key role in stabilizing the structures and affecting their hydrogen-bonding properties.
Article Abstract
The effect of fluorination on the conformational and hydrogen-bond (HB)-donating properties of a series of benzyl alcohols has been investigated experimentally by IR spectroscopy and theoretically with quantum chemical methods (ab initio (MP2) and DFT (MPWB1K)). It was found that o-fluorination generally resulted in an increase in the HB acidity of the hydroxyl group, whereas a decrease was observed upon o,o'-difluorination. Computational analysis showed that the conformational landscapes of the title compounds are strongly influenced by the presence of o-fluorine atoms. Intramolecular interaction descriptors based on AIM, NCI and NBO analyses reveal that, in addition to an intramolecular OH⋅⋅⋅F interaction, secondary CH⋅⋅⋅F and/or CH⋅⋅⋅O interactions also occur, contributing to the stabilisation of the various conformations, and influencing the overall HB properties of the alcohol group. The benzyl alcohol HB-donating capacity trends are properly described by an electrostatic potential based descriptor calculated at the MPWB1K/6-31+G(d,p) level of theory, provided solvation effects are taken into account for these flexible HB donors.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4531824 | PMC |
| http://dx.doi.org/10.1002/chem.201501171 | DOI Listing |
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