Theoretical, Solid-State, and Solution Quantification of the Hydrogen Bond-Enhanced Halogen Bond

Daniel A. Decato; Asia Marie S. Riel; James H. May; Vyacheslav S. Bryantsev; Orion B. Berryman

doi:10.1002/anie.202012262

Theoretical, Solid-State, and Solution Quantification of the Hydrogen Bond-Enhanced Halogen Bond

Daniel A. Decato, Asia Marie S. Riel, James H. May, Vyacheslav S. Bryantsev, Orion B. Berryman

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

35 Scopus citations

Abstract

Proximal noncovalent forces are commonplace in natural systems and understanding the consequences of their juxtaposition is critical. This paper experimentally quantifies for the first time a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) without the complexities of protein structure or preorganization. An HBeXB is a halogen bond that has been strengthened when the halogen donor simultaneously accepts a hydrogen bond. Our theoretical studies suggest that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond. Furthermore, stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures of halide complexes (X⁻=Br⁻, I⁻) reveal that HBeXBs produce shorter halogen bonds than non-hydrogen bond analogues. ¹⁹F NMR titrations with chloride highlight that the HBeXB analogue exhibits stronger binding. Together, these results form the foundation for future studies concerning hydrogen bonds and halogen bonds in close proximity.

Original language	English
Pages (from-to)	3685-3692
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	7
DOIs	https://doi.org/10.1002/anie.202012262
State	Published - Feb 15 2021

Funding

O.B.B., D.A.D., A.M.S.R., and J.H.M. are thankful for the support from National Science Foundation (NSF) CAREER CHE-1555324. O.B.B., D.A.D., A.M.S.R., and J.H.M. are thankful for the X-ray Core facility and NMR core facility support by the Center for Biomolecular Structure and Dynamics CoBRE (NIH NIGMS grant P20GM103546), and the University of Montana (UM). The X-ray crystallographic data were collected using a Bruker D8 Venture, principally supported by NSF MRI CHE-1337908. V.S.B. was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. O.B.B., D.A.D., A.M.S.R., and J.H.M. are thankful for the support from National Science Foundation (NSF) CAREER CHE‐1555324. O.B.B., D.A.D., A.M.S.R., and J.H.M. are thankful for the X‐ray Core facility and NMR core facility support by the Center for Biomolecular Structure and Dynamics CoBRE (NIH NIGMS grant P20GM103546), and the University of Montana (UM). The X‐ray crystallographic data were collected using a Bruker D8 Venture, principally supported by NSF MRI CHE‐1337908. V.S.B. was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE‐AC05‐00OR22725.

Funders	Funder number
CADES
Data Environment for Science
NIH NIGMS
US Department of Energy
National Science Foundation	CHE‐1555324
U.S. Department of Energy	DE‐AC05‐00OR22725
National Institute of General Medical Sciences	P20GM103546
Office of Science
Basic Energy Sciences
University of Montana	MRI CHE‐1337908
Cades Foundation
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

bond theory
halogen bonds
hydrogen bonds
noncovalent cooperativity
supramolecular chemistry

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10.1002/anie.202012262

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title = "Theoretical, Solid-State, and Solution Quantification of the Hydrogen Bond-Enhanced Halogen Bond",

abstract = "Proximal noncovalent forces are commonplace in natural systems and understanding the consequences of their juxtaposition is critical. This paper experimentally quantifies for the first time a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) without the complexities of protein structure or preorganization. An HBeXB is a halogen bond that has been strengthened when the halogen donor simultaneously accepts a hydrogen bond. Our theoretical studies suggest that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond. Furthermore, stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures of halide complexes (X−=Br−, I−) reveal that HBeXBs produce shorter halogen bonds than non-hydrogen bond analogues. 19F NMR titrations with chloride highlight that the HBeXB analogue exhibits stronger binding. Together, these results form the foundation for future studies concerning hydrogen bonds and halogen bonds in close proximity.",

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AU - Decato, Daniel A.

AU - Riel, Asia Marie S.

AU - May, James H.

AU - Bryantsev, Vyacheslav S.

AU - Berryman, Orion B.

PY - 2021/2/15

Y1 - 2021/2/15

N2 - Proximal noncovalent forces are commonplace in natural systems and understanding the consequences of their juxtaposition is critical. This paper experimentally quantifies for the first time a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) without the complexities of protein structure or preorganization. An HBeXB is a halogen bond that has been strengthened when the halogen donor simultaneously accepts a hydrogen bond. Our theoretical studies suggest that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond. Furthermore, stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures of halide complexes (X−=Br−, I−) reveal that HBeXBs produce shorter halogen bonds than non-hydrogen bond analogues. 19F NMR titrations with chloride highlight that the HBeXB analogue exhibits stronger binding. Together, these results form the foundation for future studies concerning hydrogen bonds and halogen bonds in close proximity.

AB - Proximal noncovalent forces are commonplace in natural systems and understanding the consequences of their juxtaposition is critical. This paper experimentally quantifies for the first time a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) without the complexities of protein structure or preorganization. An HBeXB is a halogen bond that has been strengthened when the halogen donor simultaneously accepts a hydrogen bond. Our theoretical studies suggest that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond. Furthermore, stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures of halide complexes (X−=Br−, I−) reveal that HBeXBs produce shorter halogen bonds than non-hydrogen bond analogues. 19F NMR titrations with chloride highlight that the HBeXB analogue exhibits stronger binding. Together, these results form the foundation for future studies concerning hydrogen bonds and halogen bonds in close proximity.

KW - bond theory

KW - halogen bonds

KW - hydrogen bonds

KW - noncovalent cooperativity

KW - supramolecular chemistry

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ER -

Theoretical, Solid-State, and Solution Quantification of the Hydrogen Bond-Enhanced Halogen Bond

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