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Title: Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes

Abstract

This paper refines the nature of the interactions between electron-deficient arenes and halide anions. Conclusions are based on (1) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (2) evaluation of crystal structures found in the Cambridge Structural Database, and (3) MP2/aug-cc-pVDZ calculations of F?, Cl?, and Br? complexes with TCB, 1,3,5-tricyanobenzene, triazine, and hexafluorobenzene. When the halide lies above the plane of the ? system, the results establish that three distinctly different types of complexes are possible: strongly covalent ? complexes, weakly covalent donor ?-acceptor complexes, and electrostatic anion-? complexes. When aryl C?H groups are present, a fourth type of interaction leads to C?H???X? hydrogen bonding. Characterization of the different geometries encountered with the four possible binding motifs provides criteria needed to design host architectures containing electron-deficient arenes. This research was performed in part using the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences laboratory, a national scientific user facility sponsored by the U.S. Department of Energy?s Office of Biological and Environmental Research located at the Pacific Northwest National Laboratory. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
899142
Report Number(s):
PNNL-SA-50328
3565; 830403000; TRN: US200706%%508
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society, 129(1):48-58
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 36 MATERIALS SCIENCE; ANIONS; BONDING; CRYSTAL STRUCTURE; DESIGN; ELECTROSTATICS; EVALUATION; HALIDES; HYDROGEN; Environmental Molecular Sciences Laboratory

Citation Formats

Berryman, Orion B., Bryantsev, Vyacheslav, Stay, David P., Johnson, Darren W., and Hay, Benjamin P. Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes. United States: N. p., 2007. Web. doi:10.1021/ja063460m.
Berryman, Orion B., Bryantsev, Vyacheslav, Stay, David P., Johnson, Darren W., & Hay, Benjamin P. Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes. United States. doi:10.1021/ja063460m.
Berryman, Orion B., Bryantsev, Vyacheslav, Stay, David P., Johnson, Darren W., and Hay, Benjamin P. Wed . "Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes". United States. doi:10.1021/ja063460m.
@article{osti_899142,
title = {Structural Criteria for the Design of Anion Receptors: The Interaction of Halides with Electron-Deficient Arenes},
author = {Berryman, Orion B. and Bryantsev, Vyacheslav and Stay, David P. and Johnson, Darren W. and Hay, Benjamin P.},
abstractNote = {This paper refines the nature of the interactions between electron-deficient arenes and halide anions. Conclusions are based on (1) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (2) evaluation of crystal structures found in the Cambridge Structural Database, and (3) MP2/aug-cc-pVDZ calculations of F?, Cl?, and Br? complexes with TCB, 1,3,5-tricyanobenzene, triazine, and hexafluorobenzene. When the halide lies above the plane of the ? system, the results establish that three distinctly different types of complexes are possible: strongly covalent ? complexes, weakly covalent donor ?-acceptor complexes, and electrostatic anion-? complexes. When aryl C?H groups are present, a fourth type of interaction leads to C?H???X? hydrogen bonding. Characterization of the different geometries encountered with the four possible binding motifs provides criteria needed to design host architectures containing electron-deficient arenes. This research was performed in part using the Molecular Science Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences laboratory, a national scientific user facility sponsored by the U.S. Department of Energy?s Office of Biological and Environmental Research located at the Pacific Northwest National Laboratory. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.},
doi = {10.1021/ja063460m},
journal = {Journal of the American Chemical Society, 129(1):48-58},
number = ,
volume = ,
place = {United States},
year = {Wed Jan 10 00:00:00 EST 2007},
month = {Wed Jan 10 00:00:00 EST 2007}
}