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The Nature of the [TTF]·+··· [TTF]·+ Interactions in the [TTF]22+ Dimers Embedded in Charged [3]Catenanes: Room-Temperature Multicenter Long Bonds.


The Nature of the [TTF]·+··· [TTF]·+ Interactions in the [TTF]22+ Dimers Embedded in Charged [3]Catenanes: Room-Temperature Multicenter Long Bonds

 

M. Capdevila-Cortada, J.J. Novoa.

Chem. Eur. J., 18 (2012) 5335.

Due to the high impact of a recent Nature Chemistry publication where diamagnetic [TTF]22+ dication dimers were obtained at room temperature by means of synthesizing a [3]catenane supramolecular entity, in this work we show an exhaustive theoretical study revealing the nature of its interactions and the stabilization of the [TTF]22+ dimer dication within the supramolecular entity. By means of DFT calculations the aforementioned [3]catenanem+ and the inclusion complex ([TTF]2n+ C CBPQT4+)m+, where CBPQT is the central macrocycle of the [3]catenane, in their different oxidation states where studied in the gas phase, solution, and solid state. Our results show the stabilization that the [TTF]n+ moieties experience when they are part of the [3]catenane, although these would not be high enough to form a [TTF]22+ dication dimer in the gas phase. On the contrary, when solvent or counterions are taken into account the whole system becomes stable. Despite the fact that this instability per se in the gase phase would make the [3]catenane dissociate, it does not since it would mean a covalent bond breaking.