Probing halogen bonding interactions between heptafluoro-2-iodopropane and three azabenzenes with Raman spectroscopy and density functional theory

Abstract

The potential formation of halogen bonded complexes between a donor, heptafluoro-2-iodopropane (HFP), and the three acceptor heterocyclic azines (azabenzenes: pyridine, pyrimidine, and pyridazine) is investigated herein through normal mode analysis...

Factors contributing to halogen bond strength and stretch or contraction of internal covalent bond

“…So the electrostatic effect is too small to counteract the bond lengthening arising from the accumulating density in the σ*(CX) antibonding orbital. C–I stretches were recently noted for XBs formed by heptafluoro-2-iodopropane with I attached to a substituted alkane, 90 similar to the elongations within the TF 3 I units noted above.…”

“…C–I stretches were also noted for heptafluoro-2-iodopropane with I attached to a substituted alkane. 90…”

“…C-I stretches were also noted for heptafluoro-2-iodopropane with I attached to a substituted alkane. 90 There has been further work which considered halogen atoms bound to atoms other than T such as N as in a halogenated succinimide 94 or directly to metal atoms. 95 When bonded simply to a F atom, the FX series of Lewis acids elongate upon complexation with NH 3 , with a corresponding Dn(FX) stretching red shift 70 but the amount of this elongation is relatively uniform from one X to the next.…”

Guest‐Host Raman under Liquid Nitrogen Spectroscopy for the Acquisition of Improved Vibrational Spectra of Solids

“…Geometry optimization and Raman vibrational frequencies and optical tensors were calculated using density functional theory with the Minnesota 06 functional M06-2X and the Pople split-valence double-ζ 6-31G** basis set. M06-2X is a global hybrid functional parametrized for nonmetals and excels in predicting noncovalent interactions; [54][55][56][57] 6-31G** features 6 primitive Gaussians with valence orbitals composed of two different basis functions for each: one with a linear combination of three Gaussian functions and the second with one Gaussian function. [58] Self-consistent reaction field (SCRF) [59] calculations were carried out via the integral equation formulism for the polarizable continuum model (IEFPCM) [60][61][62] at the same level of theory in order to compare Raman intensities.…”

Fluorescent nano-sized aggregates of halogen bonded complexes formed using perfluoropropyl iodides: a systematic comparison between two isomeric halogen bond acceptors, aniline and 4-methyl pyridine

“…On the other hand, perfluoroalkyl iodides have mostly been used as XB donors to study the related properties because of their strong s holes located on the I atom. [27][28][29] It is expected that the XB of MePy with n-C 3 F 7 I will lead to the similar wavenumber shifts of the RNMs of the pyridine ring.…”