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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, Mark
dc.contributor.authorSumby, C.
dc.date.accessioned2017-01-30T12:12:01Z
dc.date.available2017-01-30T12:12:01Z
dc.date.created2012-08-14T20:00:23Z
dc.date.issued2012
dc.identifier.citationEvans, Jack and Hollis, Courtney and Hack, Sandra and Gentleman, Alexander and Hoffmann, Peter and Buntine, Mark and Sumby, Christopher. 2012. Anion-π Interactions of Hexaaryl[3]radialenes. Journal of Physical Chemistry A. 116: pp. 8001-8007.
dc.identifier.urihttp://hdl.handle.net/20.500.11937/19129
dc.identifier.doi10.1021/jp301464s
dc.description.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.

dc.publisherAmerican Chemical Society
dc.titleAnion-π Interactions of Hexaaryl[3]radialenes
dc.typeJournal Article
dcterms.source.volume116
dcterms.source.startPage8001
dcterms.source.endPage8007
dcterms.source.issn10895639
dcterms.source.titleJournal of Physical Chemistry A
curtin.department
curtin.accessStatusFulltext not available


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