Premium
Studies of two different types of intramolecular C–H···F–C interactions from polyfluorinated diiodometal(II) diimine complexes
Author(s) -
Lu Norman,
Zheng JingHung,
Lin LeiChin,
Liu LingKang,
Chiang HsingFang,
Li TingYou,
Wen YuhSheng,
Yang ChungKuang,
Chen ShihWen,
Thrasher Joseph S.
Publication year - 2019
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201800161
Subject(s) - chemistry , intramolecular force , hydrogen bond , crystallography , diimine , metal , stereochemistry , supramolecular chemistry , crystal structure , molecule , catalysis , organic chemistry , biochemistry
The X‐ray crystal structures of the polyfluorinated complexes [5,5′‐bis(HCF 2 CF 2 CF 2 CF 2 CH 2 OCH 2 )‐2,2′‐bpy]MI 2 ( 55‐8F‐PtI 2 and 55‐8F‐PdI 2 where M = Pt and Pd, respectively) were obtained. These two structures are found to show not only two different types of intramolecular, six‐membered cyclic C–H···F–C interactions (F 2 C–H···F–C and HC–H···F–C) as important structural features but also alternating fluorinated and non‐fluorinated layers. The F 2 C–H···F–C interactions, which are close to the metal core, are much better structurally characterized in this type of complexes with fluorous ponytails at the 5,5′ positions than those previously reported at the 4,4′ positions. The molecular planes of (bpy)MI 2 are extended by self‐matching, using two C–H···I hydrogen bonds and one C–H···F–C blue‐shifting hydrogen bond. The F 2 C–H···F–C hydrogen bonds interact at the supramolecular level such that one polyfluorinated ponytail of the title compounds is transoid without an intramolecular C–H···F–C interaction, while the other polyfluorinated ponytail is cisoid with an intramolecular C–H···F–C interaction. Why one ponytail is cisoidal while the other is transoidal will be explained. Furthermore, the second type of C–H···F–C interactions involving the methylene H atom has been identified for the first time. In addition, these two metal structures are studied by density functional theory (DFT).