Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes.
Halogen bonds are a subset of noncovalent interactions with rapidly expanding applications in materials and medicinal chemistry. While halogen bonding is well known in organic compounds, it is new in the field of boron cluster chemistry. We have synthesized and crystallized carboranes containing Br atoms in two different positions, namely, bound to C- and B-vertices. The Br atoms bound to the C-vertices have been found to form halogen bonds in the crystal structures. In contrast, Br atoms bound to B-vertices formed hydrogen bonds. Quantum chemical calculations have revealed that halogen bonding in carboranes can be much stronger than in organic architectures. These findings open new possibilities for applications of carboranes, both in materials and medicinal chemistry.
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic v.v.i., Flemingovo nám. 2, 16610, Prague 6, Czech Republic.
Jindřich
http://orcid.org/0000-0002-1257-1201
J
Fanfrlík
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic v.v.i., 250 68, Řež u Prahy, Czech Republic.
Josef
J
Holub
University of Pardubice, Studentská 573, Pardubice, Czech Republic.
Zdeňka
Z
Růžičková
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic v.v.i., Flemingovo nám. 2, 16610, Prague 6, Czech Republic.
Jan
J
Řezáč
Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.|School of Engineering and Physical Sciences, Heriot-Watt University, Riccarton, Edinburgh, EH14 4AS, UK.
Paul D
PD
Lane
Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Derek A
DA
Wann
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic v.v.i., 250 68, Řež u Prahy, Czech Republic.
Drahomír
D
Hnyk
University of Pardubice, Studentská 573, Pardubice, Czech Republic.
Aleš
A
Růžička
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic v.v.i., Flemingovo nám. 2, 16610, Prague 6, Czech Republic.|Regional Center of Advanced Technologies and Materials, Department of Physical Chemistry, Palacký University, 77146, Olomouc, Czech Republic.
Pavel
P
Hobza
X-ray crystal structure; bromine; carboranes; halogen bonds; sigma holes