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|Title:||Anion-π interactions of hexaarylradialenes|
|Other Titles:||Anion-pi interactions of hexaarylradialenes|
|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|
|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 hexaarylradialene compounds exhibit intriguing structures with short anion to π-centroid distances in the solid-state. Furthermore, these radialene compounds display useful photophysical and electrochemical properties that make them ideal as potential platforms for anion receptors. In this study, hexafluororadialene 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. Hexafluororadialene 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 hexafluororadialene with halide anions were calculated and found to be favorable and equivalent to those of fluorinated aromatic compounds. A series of synthetically accessible hexaarylradialenes 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 hexaarylradialenes also show large positive Qzz quadrupole moments and two areas of positive potential; at the radialene core and the acidic aryl hydrogen atoms. The interaction energies of the complexes of hexaarylradialenes and halide anions were found to follow the trend F(-) > Cl(-) ≈ Br(-) and correlate with the electron-deficient nature of the 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 hexaarylradialenes with F(-), Cl(-), and Br(-) predicted computationally. Anion-radialene complexes were successfully detected, and the stability of the complexes in tandem MS/MS experiments was found to support the computational results.|
|Rights:||Copyright © 2012 American Chemical Society|
|Appears in Collections:||Aurora harvest 5|
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