Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

TY - JOUR

T1 - Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

AU - Fanfrlík, Jindřich

AU - Holub, Josef

AU - Růžičková, Zdeňka

AU - Řezáč, Jan

AU - Lane, Paul D.

AU - Wann, Derek A.

AU - Hnyk, Drahomír

AU - Růžička, Aleš

AU - Hobza, Pavel

N1 - © 2016 John Wiley & Sons, Inc. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2016/11/4

Y1 - 2016/11/4

N2 - 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.

AB - 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.

KW - bromine

KW - carboranes

KW - halogen bonds

KW - sigma holes

KW - X-ray crystal structure

UR - http://www.scopus.com/inward/record.url?scp=84994351590&partnerID=8YFLogxK

U2 - 10.1002/cphc.201600848

DO - 10.1002/cphc.201600848

M3 - Article

C2 - 27595561

SN - 1439-4235

VL - 17

SP - 3373

EP - 3376

JO - ChemPhysChem

JF - ChemPhysChem

IS - 21

ER -