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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}
}
  • This paper refines the nature of the interactions between electron-deficient arenes and halide anions. Conclusions are based on (i) new crystal structures containing alkali halide salts with 1,2,4,5-tetracyanobenzene (TCB) and 18-crown-6, (ii) evaluation of crystal structures found in the Cambridge Structural Database, and (iii) 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 pi system, the results establish that three distinctly different types of complexes are possible: strongly covalent sigma complexes, weakly covalent donor-pi-acceptor complexes, and noncovalent anion-pi complexes. When aryl C-H groups are present, amore » fourth type of interaction leads to C-H center dot center dot center dot 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.« less
  • The arrangement of urea ligands about different shaped anions has been evaluated with electronic structure calculations. Geometries and binding energies are reported for urea complexes with Cl{sup -}, NO{sub 3}{sup -}, and ClO{sub 4}{sup -}. The results yield new insight into the nature of urea-anion interactions and provide structural criteria for the deliberate design of anion selective receptors containing two or more urea donor groups.
  • Molecular hosts for anion complexation are often constructed by combining two or more hydrogen bonding functional groups, D–H. The deliberate design of complementary host architectures requires knowledge of the optimal geometry for the hydrogen bonds formed between the host and the guest. Herein, we present a detailed study of the structural aspects of hydrogen bonding interactions with the NO3– anion. A large number of crystal structures are analyzed to determine the number of hydrogen bond contacts per anion and to further characterize the structural aspects of these interactions. Electronic structure calculations are used to determine stable geometries and interaction energiesmore » for NO3– complexes with several simple molecules possessing D–H groups, including water, methanol, N-methylformamide, and methane. Theoretical results are reported at several levels of density functional theory, including BP86/DN**, B3LYP/TZVP, and B3LYP/TZVP+, and at MP2/aug-cc-pVDZ. In addition, MP2 binding energies for these complexes were obtained at the complete basis set limit by extrapolating from single point energies obtained with larger correlation-consistent basis sets. The results establish that NO3– has an intrinsic hydrogen bonding topography in which there are six optimal sites for proton location. The structural features observed in crystal structures and in the optimized geometries of complexes are explained by a preference to locate the D–H protons in these positions. For the strongest hydrogen bonding interactions, the N–O•••H angle is bent at an angle of 115 ± 10°, and the hydrogen atom lies in the NO3– plane giving O–N–O•••H dihedral angles of 0 and 180°. In addition, the D-H vector points towards the oxygen atom, giving D–H•••O angles that are near linear, 170 ± 10°. Due to steric hindrance, simple alcohol O–H and amide N–H donors form 3:1 complexes with NO3–, with H•••O distances of 1.85 ± 0.5 Å. Thus, the optimal cavity radius for a tridentate host, defined as the distance from the center to the D–H hydrogen atoms, is 2.65 ± 0.15 Å.« less
  • The crystal structure of the anion-deficient manganites La{sub 0.7}Sr{sub 0.3}MnO{sub 3-{delta}} ({delta} = 0, 0.10, 0.15, 0.20) is investigated using high-resolution neutron diffraction. At room temperature, the crystal structure of the stoichiometric manganite La{sub 0.7}Sr{sub 0.3}MnO{sub 3} and the anion-deficient manganite La{sub 0.7}Sr{sub 0.3}MnO{sub 2.9} is satisfactorily described in rhombohedral space group R3-barc. The anion-deficient manganite La{sub 0.7}Sr{sub 0.3}MnO{sub 2.85} is characterized by two perovskite phases with space groups R3-barc and 14/mcm. The crystal structure of the La{sub 0.7}Sr{sub 0.3}MnO{sub 2.8} manganite corresponds to the structure of a perovskite phase with space group I4/mcm. It is established that the phasemore » separation in the crystal structure of the La{sub 0.7}Sr{sub 0.3}MnO{sub 3-{delta}} manganites at a temperature of 293 K is associated with a nonuniform distribution of oxygen vacancies.« less
  • The results of neutron diffraction studies of the La{sub 0.70}Sr{sub 0.30}MnO{sub 2.85} compound and its behavior in an external magnetic field are stated. It is established that in the 4-300 K temperature range, two structural perovskite phases coexist in the sample, which differ in symmetry (groups R3-bar c and I4/mcm). The reason for the phase separation is the clustering of oxygen vacancies. The temperature (4-300 K) and field (0-140 kOe) dependences of the specific magnetic moment are measured. It is found that in zero external field, the magnetic state of La{sub 0.70}Sr{sub 0.30}MnO{sub 2.85} is a cluster spin glass, whichmore » is the result of frustration of Mn{sup 3+}-O-Mn{sup 3+} exchange interactions. An increase in external magnetic field up to 10 kOe leads to fragmentation of ferromagnetic clusters and then to an increase in the degree of polarization of local spins of manganese and the emergence of long-range ferromagnetic order. With increasing magnetic field up to 140 kOe, the magnetic ordering temperature reaches 160 K. The causes of the structural and magnetic phase separation of this composition and formation mechanism of its spin-glass magnetic state are analyzed.« less