title: Decorating tetrathiafulvalene (TTF) with fluorinated phenyls through sulfur bridges: facile synthesis, properties, and aggregation through fluorine interactions.
abstract: Tetrathiafulvalene derivatives (TTF1-TTF9) bearing fluorinated phenyl groups attached through the sulfur bridges have been synthesized by employing a copper-mediated C-S coupling reaction of C6 H5-x Fx I (x=1, 2, 5) and a zinc-thiolate complex, (TBA)2 [Zn(DMIT)2 ] (TBA=tetrabutyl ammonium, DMIT=1,3-dithiole-2-thione-4,5-dithiolate), as the key step. Particularly, the selective synthesis of C6 F5 -substituted (TTF8) and C6 F4 -fused (TTF9) TTFs from C6 F5 I is disclosed. The physicochemical properties and crystal structures of these TTFs are fully investigated by UV/Vis absorption spectra, cyclic voltammetry, molecular orbital calculation, and single-crystal X-ray diffraction. The exchange of hydrogen versus fluorine on the peripheral phenyl groups show a notable influence on both the electronic and crystallographic natures of the resulting TTFs: 1) lowering both the HOMO and the LUMO energy levels, 2) modulating the electrochemical properties by regioselective and/or the degree of fluorination, 3) enhancing the driving forces of stacking by multiple fluorine interactions (F⋅⋅⋅S, CF⋅⋅⋅π/πF , CF⋅⋅⋅FC, and CF⋅⋅⋅H). This work indicates that the decoration with fluorinated phenyls holds promise to produce functional TTFs with novel electronic and aggregation features.
authors: State Key Laboratory of Applied Organic Chemistry & School of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu Province (P.R. China).
authors: Xiaofeng
authors: X
authors: Lu
authors: Jibin
authors: J
authors: Sun
authors: Yu
authors: Y
authors: Liu
authors: Jiafeng
authors: J
authors: Shao
authors: Longfei
authors: L
authors: Ma
authors: Shangxi
authors: S
authors: Zhang
authors: Jinlian
authors: J
authors: Zhao
authors: Yongliang
authors: Y
authors: Shao
authors: Hao-Li
authors: HL
authors: Zhang
authors: Zhaohui
authors: Z
authors: Wang
authors: Xiangfeng
authors: X
authors: Shao
keywords: C-S coupling; TTF derivatives; electrochemistry; fluorine interactions; photochemistry