Quantitative Assessment of Halogen Bonding Utilizing Vibrational Spectroscopy

摘要: A total of 202 halogen-bonded complexes have been studied using a dual-level approach: ωB97XD/aug-cc-pVTZ was used to determine geometries, natural bond order charges, charge transfer, dipole moments, electron and energy density distributions, vibrational frequencies, local stretching force constants, relative strength orders n. The accuracy these calculations checked for subset at the CCSD(T)/aug-cc-pVTZ level theory. Apart from this, all binding energies were verified CCSD(T) level. 10 different electronic effects identified that contribute halogen bonding explain variation in its intrinsic strength. Strong bonds are found systems with three-center-four-electron (3c-4e) such as chlorine donors interaction substituted phosphines. If is supported by hydrogen bonding, genuine 3c-4e can be realized. Perfluorinated diiodobenzenes form relatively strong alkylamines as...