Understanding the Forces That Govern Packing: A Density Functional Theory and Structural Investigation of Anion-pi-Anion and Nonclassical C-H···Anion Interactions

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dc.contributor.author Brooker, Sally
dc.contributor.author White, Nicholas G.
dc.contributor.author Bauzá Riera, Antonio
dc.contributor.author Deyà, Pere Maria
dc.contributor.author Frontera Beccaria, Antonio
dc.date.accessioned 2018-09-21T11:58:10Z
dc.identifier.uri http://hdl.handle.net/11201/147589
dc.description.abstract [eng] The ability of Ni(II) coordinated 4-pyrrolyl-3,5-di(2- pyridyl)-1,2,4-triazole (pldpt) to establish multiple anion−π interactions is analyzed. Experimentally, such complexes were previously shown to form strong anion−π interactions, including "π-pocket" and "π-sandwiched" motifs, in the crystal lattice. In the latter, the triazole ring is "sandwiched" by two anions forming a ternary anion−π−anion assembly (π-sandwich) which, surprisingly, gave about 0.2 Å shorter anion−π distances than in binary assemblies (where only one side of the triazole participates in the anion binding), indicating the possibility of cooperativity. In depth analysis, using dispersion-corrected density functional theory (DFT, BP86-D/def2-TZVP level of theory), shows that this ternary anion−π−anion interaction is slightly less energetically favorable than the binary anion−π interactions in isolation. Hence, the sandwich interaction is not cooperative (Ecoop is positive), but, as Ecoop contributes less than 1.5% of the total interaction energy (which is dominated by the strong electrostatic attraction of the anions to the highly π-acidic Ni(II)-coordinated triazole ring), the presence of nonclassical C−H···anion hydrogen bonds can offset this, making the short anion−π sandwich interactions the most favorable solid state conformation.
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dc.relation.isformatof Versió postprint del document publicat a: https://doi.org/10.1021/ic30146881
dc.relation.ispartof Inorganic Chemistry, 2012, vol. 51, num. 19, p. 10334-10340
dc.subject.classification 54 - Química
dc.subject.other 54 - Chemistry. Crystallography. Mineralogy
dc.title Understanding the Forces That Govern Packing: A Density Functional Theory and Structural Investigation of Anion-pi-Anion and Nonclassical C-H···Anion Interactions
dc.type info:eu-repo/semantics/article
dc.type info:eu-repo/semantics/acceptedVersion
dc.date.updated 2018-09-21T11:58:10Z
dc.date.embargoEndDate info:eu-repo/date/embargoEnd/2075-01-01
dc.embargo 2075-01-01
dc.rights.accessRights info:eu-repo/semantics/embargoedAccess
dc.identifier.doi https://doi.org/10.1021/ic30146881


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