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- Title
Activating both Halogen and Chalcogen Bonding Interactions in Cation Radical Salts of Iodinated Tetrathiafulavalene Derivatives.
- Authors
Beau, Maxime; Jeannin, Olivier; Lee, Sunhee; Barrière, Frédéric; Fourmigué, Marc; Jeon, Ie‐Rang
- Abstract
Halogen bonding (XB) interactions are investigated in cation radical salts of bis(methylthio)‐5,5'‐diiodotetrathiafulvalene (1). Electrocrystallization of 1 in the presence of Bu4NCl affords a 1 : 1 salt formulated as (E‐1)Cl. Particularly strong I⋅⋅⋅Cl− XB interactions are observed around the Cl− anion with the distances at 78 % the sum of the van der Waals radii, a consequence of the XB charge activation in the cation radical. Moreover, the Cl− environment is complemented by two extra S⋅⋅⋅Cl− chalcogen bonding (ChB) interactions, an original feature among reported halide salts of TTF derivatives. Electrostatic potential calculations on the cation radical further demonstrate the efficient activation of the S atoms of the 1,3‐dithiole rings (Vs,max=87.2 kcal/mol), as strong as with the iodine atoms (Vs,max=87.9 kcal/mol). The radical cations form weakly dimerized stacks, as confirmed by the variable‐temperature magnetic susceptibility and the weak conductivity (4.8×10−5 S cm−1).
- Subjects
RADICAL cations; RADICAL anions; HALOGENS; ELECTRIC potential; MAGNETIC susceptibility; SALTS; ELECTROCRYSTALLIZATION; VAN der Waals forces
- Publication
ChemPlusChem, 2020, Vol 85, Issue 9, p2136
- ISSN
2192-6506
- Publication type
Article
- DOI
10.1002/cplu.202000500