Anion-π Interactions of Hexaaryl[3]radialenes
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...
| Main Authors: | , , , , , , |
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| Format: | Journal Article |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/20.500.11937/19129 |
| _version_ | 1848749944932925440 |
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| author | Evans, J. Hollis, C. Hack, S. Gentleman, A. Hoffmann, P. Buntine, Mark Sumby, C. |
| author_facet | Evans, J. Hollis, C. Hack, S. Gentleman, A. Hoffmann, P. Buntine, Mark Sumby, C. |
| author_sort | Evans, J. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T07:28:59Z |
| format | Journal Article |
| id | curtin-20.500.11937-19129 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T07:28:59Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| recordtype | eprints |
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| spelling | curtin-20.500.11937-191292017-09-13T15:42:44Z Anion-π Interactions of Hexaaryl[3]radialenes Evans, J. Hollis, C. Hack, S. Gentleman, A. Hoffmann, P. Buntine, Mark Sumby, C. 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. 2012 Journal Article http://hdl.handle.net/20.500.11937/19129 10.1021/jp301464s American Chemical Society restricted |
| spellingShingle | Evans, J. Hollis, C. Hack, S. Gentleman, A. Hoffmann, P. Buntine, Mark Sumby, C. Anion-π Interactions of Hexaaryl[3]radialenes |
| title | Anion-π Interactions of Hexaaryl[3]radialenes |
| title_full | Anion-π Interactions of Hexaaryl[3]radialenes |
| title_fullStr | Anion-π Interactions of Hexaaryl[3]radialenes |
| title_full_unstemmed | Anion-π Interactions of Hexaaryl[3]radialenes |
| title_short | Anion-π Interactions of Hexaaryl[3]radialenes |
| title_sort | anion-π interactions of hexaaryl[3]radialenes |
| url | http://hdl.handle.net/20.500.11937/19129 |