Please use this identifier to cite or link to this item: https://hdl.handle.net/2440/71991
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dc.contributor.authorEvans, J.-
dc.contributor.authorHollis, C.-
dc.contributor.authorHack, S.-
dc.contributor.authorGentleman, A.-
dc.contributor.authorHoffmann, P.-
dc.contributor.authorBuntine, M.-
dc.contributor.authorSumby, C.-
dc.date.issued2012-
dc.identifier.citationThe Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2012; 116(30):8001-8007-
dc.identifier.issn1089-5639-
dc.identifier.issn1520-5215-
dc.identifier.urihttp://hdl.handle.net/2440/71991-
dc.description.abstractCoordination 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.-
dc.description.statementofresponsibilityJack D Evans, Courtney A Hollis, Sandra Hack, Alexander Gentleman, Peter Hoffmann, Mark Anthony Buntine, and Christopher J. Sumby-
dc.language.isoen-
dc.publisherAmer Chemical Soc-
dc.rightsCopyright © 2012 American Chemical Society-
dc.subjectCross-conjugated compounds-
dc.subjecthexaaryl[3]radialenes-
dc.subjectanion-π interactions-
dc.subjectcomputational chemistry-
dc.subjectmass spectrometry.-
dc.titleAnion-π interactions of hexaaryl[3]radialenes-
dc.title.alternativeAnion-pi interactions of hexaaryl[3]radialenes-
dc.typeJournal article-
dc.identifier.doi10.1021/jp301464s-
pubs.publication-statusPublished-
dc.identifier.orcidEvans, J. [0000-0001-9521-2601]-
dc.identifier.orcidSumby, C. [0000-0002-9713-9599]-
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