Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction

Abstract

The vicinal substituents, with gauche/stagger isomer in CH2XCH2F and cis/trans isomer in CHXCHF, affect the interaction of C(spn)–F⋯H–O organofluorine hydrogen bonds differently.

Effects of Electronic Structure of Adjacent Carbon on the Strength of C─F⋯H─F Organofluorine Hydrogen Bonds

“…Unsurprisingly, the enhancement of the proximal lone pair electrons on the strength of organofluorine hydrogen bond is larger than that of the vicinal ones (see Table 1, CE-a-1 vs CE-a-2-F, CE-a-3 vs CE-a-4-F). As is consistent with our previous studies, [18] the vicinal F substituent slightly reduces the strength of organofluorine hydrogen bond. Comparing the interaction energy between CE-a-1 and CE-a-3, we found that the direction of the vicinal lone pair electron has little effect on the strength of organofluorine hydrogen bond.…”

“…We found that the electron‐withdrawing substituents on the vicinal carbon could also reduce the ability of F atom as hydrogen bond acceptor, but the degree of weakening is small. The effect of vicinal F‐, Cl‐, and Br‐substituent on the strength of C─F⋯H─O is comparative …”

“…The effect of vicinal F-, Cl-, and Br-substituent on the strength of C─FÁ Á ÁH─O is comparative. [18] Although many studies have been done for the properties of the organofluorine hydrogen bond, including its energetics, spectral characteristics, we are still not clear which properties of the fluorine atom in C─F are important on the strength of organofluorine hydrogen bond. The further exploration of its primary factors needs to be done for a better understanding of the organofluorine hydrogen bonding.…”

The role of substituted pyridine Schiff bases as ancillary ligands in the optical properties of a new series of fac-rhenium(i) tricarbonyl complexes: a theoretical view

“…This result can be explained by the presence of halogen substitutions, particularly at position 6 of the phenolic ring, which enhances the electronwithdrawing effect (inductive effect 88-91 ). Furthermore, the presence of the halogen could participate in forming a halogencarbon permanent dipole, favoring the interaction with the vicinal OH group in the phenolic ring (as previously reported 92,93 ) (Fig. 5), potentially affecting the photoluminescent behavior (see below).…”

Design of functional binders for high-specific-energy lithium-ion batteries: from molecular structure to electrode properties

“…14 Due to partial substitution of H atoms with F atoms in the vinylidene fluoride monomer compared with ethylene, PVDF possesses superior chemical, electrochemical, and thermal stability due to the higher bond energy of C–F bonds than C–H bonds. 15 The electrochemical window of PVDF is about 5 V and the thermal decomposition temperature is up to 400 °C. 16 Meanwhile, the presence of H is beneficial for the formation of hydrogen bonds (C–H⋯F or O–H⋯F).…”