dc.contributor.author |
Aragay, Gemma
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dc.contributor.author |
Frontera Beccaria, Antonio
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dc.contributor.author |
Lloveras, Vega
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dc.contributor.author |
Vidal-Gancedo, José
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dc.contributor.author |
Ballester Balaguer, Pablo José
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dc.date.accessioned |
2018-10-09T10:37:15Z |
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dc.identifier.uri |
http://hdl.handle.net/11201/148007 |
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dc.description.abstract |
[eng] We report experimental evidence indicating that the nature of the interaction established between HAT(CN)6, a well-known strong electron acceptor aromatic compound, with mono- or polyatomic anions switches from the almost exclusive formation of reversible anion−π complexes, featuring a markedly charge transfer (CT) or formal electron-transfer (ET) character, to the quantitative and irreversible net production of the anion radical [HAT(CN)6] − and the dianion [HAT(CN)6]2− species. The preferred mode of interaction is dictated by the electron donor abilities of the interacting anion. Thus, weaker Lewis basic anions such as Br− or I− are prone to form mainly anion−π complexes. On the contrary, stronger Lewis basic F− or −OH anions display a net ET process. The ET process can be either thermal or photoinduced depending on the HOMO/LUMO energy difference between the electron donor (anion) and the electron acceptor (HAT(CN)6). These ET processes possibly involve the intermediacy of anion−π complexes having strong ET character and producing an ion-pair radical complex. We hypothesize that the irreversible dissociation of the pair of radicals forming the solvent-caged complex is caused by the reduced stability (high reactivity) of the radical resulting from the anion. |
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dc.format |
application/pdf |
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dc.relation.isformatof |
Versió postprint del document publicat a: https://doi.org/10.1021/ja309960m |
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dc.relation.ispartof |
Journal of the American Chemical Society, 2013, vol. 135, p. 2620-2627 |
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dc.rights |
(c) American Chemical Society , 2013 |
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dc.subject.classification |
54 - Química |
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dc.subject.other |
54 - Chemistry. Crystallography. Mineralogy |
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dc.title |
The different nature of the interactions between anions and HAT(CN)6: from reversible anion-pi complexes to irreversible electron transfer processes (HAT(CN)6 = 1,4,5,8,9,12-hexaazatriphenylene) |
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dc.type |
info:eu-repo/semantics/article |
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dc.type |
info:eu-repo/semantics/acceptedVersion |
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dc.date.updated |
2018-10-09T10:37:15Z |
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dc.date.embargoEndDate |
info:eu-repo/date/embargoEnd/2075-01-01 |
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dc.embargo |
2075-01-01 |
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dc.rights.accessRights |
info:eu-repo/semantics/embargoedAccess |
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dc.identifier.doi |
https://doi.org/10.1021/ja309960m |
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