Please use this identifier to cite or link to this item: https://hdl.handle.net/2440/71991
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Type: Journal article
Title: Anion-π interactions of hexaaryl[3]radialenes
Other Titles: Anion-pi interactions of hexaaryl[3]radialenes
Author: Evans, J.
Hollis, C.
Hack, S.
Gentleman, A.
Hoffmann, P.
Buntine, M.
Sumby, C.
Citation: The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2012; 116(30):8001-8007
Publisher: Amer Chemical Soc
Issue Date: 2012
ISSN: 1089-5639
1520-5215
Statement of
Responsibility: 
Jack D Evans, Courtney A Hollis, Sandra Hack, Alexander Gentleman, Peter Hoffmann, Mark Anthony Buntine, and Christopher J. Sumby
Abstract: Coordination polymers and discrete metallo-supramolecular assemblies of hexaaryl[3]radialene compounds exhibit intriguing structures with short anion to π-centroid distances in the solid-state. Furthermore, these [3]radialene compounds display useful photophysical and electrochemical properties that make them ideal as potential platforms for anion receptors. In this study, hexafluoro[3]radialene was optimized to the MP2/aug-cc-pVTZ level of theory, and its complexes with halide anions were optimized to HF/6-31G++(d,p), MP2/6-31G++(d,p), M06-2X/6-31G++(d,p), and M06-2X/6-311G++(d,p) levels of theory. Hexafluoro[3]radialene was shown to have properties (large positive Qzz and areas of positive electrostatic surface potential) comparable to other compounds that show anion-π interactions. The interaction energies of complexes of hexafluoro[3]radialene with halide anions were calculated and found to be favorable and equivalent to those of fluorinated aromatic compounds. A series of synthetically accessible hexaaryl[3]radialenes were optimized to HF/6-31G++(d,p) theory and their complexes with halides optimized to the M06-2X/6-31G++(d,p) level of theory. The calculated properties of the electron-deficient hexaaryl[3]radialenes also show large positive Qzz quadrupole moments and two areas of positive potential; at the [3]radialene core and the acidic aryl hydrogen atoms. The interaction energies of the complexes of hexaaryl[3]radialenes and halide anions were found to follow the trend F(-) > Cl(-) ≈ Br(-) and correlate with the electron-deficient nature of the [3]radialene. Close contacts were observed between the anion and the radialene core and the aryl hydrogen atoms, suggesting a combination of anion-π and hydrogen bonding is important. Mass spectrometry was used to experimentally observe the complexes of a number of hexaaryl[3]radialenes with F(-), Cl(-), and Br(-) predicted computationally. Anion-[3]radialene complexes were successfully detected, and the stability of the complexes in tandem MS/MS experiments was found to support the computational results.
Keywords: Cross-conjugated compounds
hexaaryl[3]radialenes
anion-π interactions
computational chemistry
mass spectrometry.
Rights: Copyright © 2012 American Chemical Society
DOI: 10.1021/jp301464s
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