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https://hdl.handle.net/2440/71991
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dc.contributor.author | Evans, J. | - |
dc.contributor.author | Hollis, C. | - |
dc.contributor.author | Hack, S. | - |
dc.contributor.author | Gentleman, A. | - |
dc.contributor.author | Hoffmann, P. | - |
dc.contributor.author | Buntine, M. | - |
dc.contributor.author | Sumby, C. | - |
dc.date.issued | 2012 | - |
dc.identifier.citation | The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2012; 116(30):8001-8007 | - |
dc.identifier.issn | 1089-5639 | - |
dc.identifier.issn | 1520-5215 | - |
dc.identifier.uri | http://hdl.handle.net/2440/71991 | - |
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.description.statementofresponsibility | Jack D Evans, Courtney A Hollis, Sandra Hack, Alexander Gentleman, Peter Hoffmann, Mark Anthony Buntine, and Christopher J. Sumby | - |
dc.language.iso | en | - |
dc.publisher | Amer Chemical Soc | - |
dc.rights | Copyright © 2012 American Chemical Society | - |
dc.source.uri | http://dx.doi.org/10.1021/jp301464s | - |
dc.subject | Cross-conjugated compounds | - |
dc.subject | hexaaryl[3]radialenes | - |
dc.subject | anion-π interactions | - |
dc.subject | computational chemistry | - |
dc.subject | mass spectrometry. | - |
dc.title | Anion-π interactions of hexaaryl[3]radialenes | - |
dc.title.alternative | Anion-pi interactions of hexaaryl[3]radialenes | - |
dc.type | Journal article | - |
dc.identifier.doi | 10.1021/jp301464s | - |
pubs.publication-status | Published | - |
dc.identifier.orcid | Evans, J. [0000-0001-9521-2601] | - |
dc.identifier.orcid | Gentleman, A. [0000-0003-3830-2488] | - |
dc.identifier.orcid | Sumby, C. [0000-0002-9713-9599] | - |
Appears in Collections: | Aurora harvest 5 Environment Institute publications IPAS publications |
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