Beau Maxime, Jeannin Olivier, Lee Sunhee, Barrière Frédéric, Fourmigué Marc, Jeon Ie-Rang
Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes), Campus de Beaulieu, 35000, Rennes, France.
Department of Chemistry, Seoul Women's University, Seoul, 01797 (Republic of, Korea.
Chempluschem. 2020 Sep;85(9):2136-2142. doi: 10.1002/cplu.202000500. Epub 2020 Aug 28.
Halogen bonding (XB) interactions are investigated in cation radical salts of bis(methylthio)-5,5'-diiodotetrathiafulvalene (1). Electrocrystallization of 1 in the presence of Bu NCl 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 (V =87.2 kcal/mol), as strong as with the iodine atoms (V =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 S cm ).
研究了双（甲硫基）-5,5'-二碘四硫富瓦烯（1）的阳离子自由基盐中的卤键（XB）相互作用。在Bu₄NCl存在下，1进行电结晶得到一种化学式为（E-1）Cl的1:1盐。在Cl⁻阴离子周围观察到特别强的I⋅⋅⋅Cl XB相互作用，其距离为范德华半径之和的78%，这是阳离子自由基中XB电荷活化的结果。此外，Cl的环境还通过另外两个S⋅⋅⋅Cl硫属元素键（ChB）相互作用得到补充，这是TTF衍生物报道的卤化物盐中的一个原始特征。对阳离子自由基的静电势计算进一步证明了1,3-二硫杂环戊烯环中S原子的有效活化（V = 87.2 kcal/mol），与碘原子的活化强度相当（V = 87.9 kcal/mol）。自由基阳离子形成弱二聚化堆叠，变温磁化率和弱电导率（4.8×10⁻³ S cm⁻¹）证实了这一点。
