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Unusual H‐Bond Topology and Bifurcated H‐bonds in the 2‐Fluoroethanol Trimer
Author(s) -
Thomas Javix,
Liu Xunchen,
Jäger Wolfgang,
Xu Yunjie
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201505934
Subject(s) - trimer , topology (electrical circuits) , chirality (physics) , molecule , single bond , chemistry , lone pair , natural bond orbital , hydrogen bond , computational chemistry , chemical physics , crystallography , dimer , physics , organic chemistry , quantum mechanics , group (periodic table) , chiral symmetry , mathematics , combinatorics , nambu–jona lasinio model , quark
By using a combination of rotational spectroscopy and ab initio calculations, an unusual H‐bond topology was revealed for the 2‐fluoroethanol trimer. The trimer exhibits a strong heterochiral preference and adopts an open OH⋅⋅⋅OH H‐bond topology while utilizing two types of bifurcated H‐bonds involving organic fluorine. This is in stark contrast to the cyclic OH⋅⋅⋅OH H‐bond topology adopted by trimers of water and other simple alcohols. The strengths of different H‐bonds in the trimer were analyzed by using the quantum theory of atoms in molecules. The study showcases a remarkable example of a chirality‐induced switch in H‐bond topology in a simple transient chiral fluoroalcohol. It provides important insight into the H‐bond topologies of small fluoroalcohol aggregates, which are proposed to play a key role in protein folding and in enantioselective reactions and separations where fluoroalcohols serve as a (co)solvent.