Decorating Tetrathiafulvalene (TTF) with Fluorinated Phenyls through Sulfur Bridges: Facile Synthesis, Properties, and Aggregation through Fluorine Interactions. Issue 31 (30th June 2014)

• Record Type: Journal Article
• Authors: Lu, Xiaofeng; Sun, Jibin; Liu, Yu; Shao, Jiafeng; Ma, Longfei; Zhang, Shangxi; Zhao, Jinlian; Shao, Yongliang; Zhang, Hao‐Li; Wang, Zhaohui; Shao, Xiangfeng
• Is Part Of: Chemistry. Volume 20:Issue 31(2014)
• Page Start: 9650
• Page End: 9656
• Publication Date: 2014-06-30
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201402327
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Tetrathiafulvalene derivatives (<bold>TTF1</bold>–<bold>TTF9</bold>) bearing fluorinated phenyl groups attached through the sulfur bridges have been synthesized by employing a copper‐mediated C–S coupling reaction of C<sub>6</sub>H<sub>5−<italic>x</italic></sub>F<sub><italic>x</italic></sub>I (<italic>x</italic>=1, 2, 5) and a zinc‐thiolate complex, (TBA)<sub>2</sub>[Zn(DMIT)<sub>2</sub>] (TBA=tetrabutyl ammonium, DMIT=1, 3‐dithiole‐2‐thione‐4, 5‐dithiolate), as the key step. Particularly, the selective synthesis of C<sub>6</sub>F<sub>5</sub>‐substituted (<bold>TTF8</bold>) and C<sub>6</sub>F<sub>4</sub>‐fused (<bold>TTF9</bold>) TTFs from C<sub>6</sub>F<sub>5</sub>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/π<sub>F</sub>, 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.</p> </abstract>