The Origin of the Room‐Temperature Stability of [TTF].+⋅⋅⋅[TTF].+ Long,Multicenter Bonds Found in Functionalized π‐[R‐TTF]22+ Dimers Included in the Cucurbit[8]uril Cavity |
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| Authors: | Marçal Capdevila‐Cortada Prof. Joel S. Miller Prof. Juan J. Novoa |
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| Affiliation: | 1. Departament de Química Física and IQTCUB, Facultat de Química, Universitat de Barcelona, Av. Diagonal 647, 08028‐Barcelona (Spain);2. Department of Chemistry, University of Utah, Salt Lake City, UT 84112‐0850 (USA) |
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| Abstract: | A computational study is performed to identify the origin of the room‐temperature stability, in aqueous solution, of functionalized π‐[R‐TTF]22+ dimers (TTF=tetrathiafulvalene; R=(CH2OCH2)5CH2OH) included in the cavity of a cucurbit[8]uril (CB[8]) molecule. π‐[R‐TTF]22+ dimers in pure water are weakly stable, and are mostly dissociated at room temperature. Upon addition of CB[8] to an aqueous π‐[R‐TTF]22+ solution, a (π‐[R‐TTF]2?CB[8])2+ inclusion complex is formed. The same complex is obtained after the sequential inclusion of two [R‐TTF].+ monomers in the CB[8] molecule. Both processes are thermodynamically and kinetically allowed. π‐[R‐TTF]22+ dimers dissolved in pure water present a [TTF].+???[TTF].+ long, multicenter bond, similar to that already identified in π‐[TTF]22+ dimers dissolved in organic solvents. Upon their inclusion in CB[8], the strength and other features of the [TTF].+???[TTF].+ long, multicenter bond are preserved. The room temperature stability of the π‐[R‐TTF]22+ dimers included in CB[8] is shown to originate in the π‐[R‐TTF]22+???CB[8] interaction, the strength of which comes from a strongly attractive electrostatic component and a dispersion component. Such a dominant electrostatic term is caused by the strongly polarized charge distribution in CB[8], the geometrical complementarity of the π‐[R‐TTF]22+ and CB[8] geometries, and the amplifying effect of the 2+ charge in π‐[R‐TTF]22+. |
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| Keywords: | density functional calculations dimerization host– guest systems inclusion compounds supramolecular chemistry |
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