# Synthesis, Characterization, and Self-Assembly of a Tetrathiafulvalene (TTF)-Triglycyl Derivative
## 2 Materials and Methods
### Synthesis and Characterization of Compounds
#### 2.2.2 Synthetic Procedures and Characterization of Compounds  
_4,5-Bis-(butylthio)-1,3-dithiole-2-thione_ (**3**): A mixture of _bis_(tetrabutylammonium) _bis_(1,3-dithiole-2-thione-4,5-dithiolate) zinc (**1**, TCI chemicals) (2.18 g, 2.30 mmol) and 1-bromobutane (**2**, Sigma-Aldrich) (1.24 mL, 11.50 mmol) in anhydrous acetonitrile (ACN) (30 mL) was refluxed for 1 h. The initially formed reddish solution turned into a green-yellowish mixture. Once the solution was cooled to room temperature (RT), the precipitate was filtered out and the solution mixture was concentrated to dryness under reduced pressure. The residue was dissolved in dichloromethane (DCM) (50 mL) and the organic phase was washed with water (4 \(\times\) 30 mL). The organic phase was dried over anhydrous MgSO\({}_{4}\) and concentrated to dryness under reduced pressure. The residue was purified by flash chromatography on silica gel (hexane/ethyl acetate (AcOEt) 1:1) affording the desired compound **3** as reddish oil (1.40 g, 98% yield). TLC in AcOEt/hexane 10:0.1, R\({}_{f}\) = 0.85. \({}^{1}\)H-NMR (400 MHz, CDCl\({}_{3}\)) \(\delta\) (ppm): 2.85 (t, \(J\) = 7.3 Hz, 4H, = C-SCH\({}_{2}\)-), 1.67-1.59 (m, 4H, = C-SCH\({}_{2}\)-CH\({}_{2}\)-), 1.48-1.38 (m, 4H, = C-SCH\({}_{2}\)-CH\({}_{2}\)-), 0.91 (t, \(J\) = 7.3 Hz, 6H, CH\({}_{3}\)). \({}^{13}\)C-NMR (100 MHz, CDCl\({}_{3}\)) \(\delta\) (ppm): 211.49 (C-S), 136.34 (S-C-S), 36.42 (S-CH\({}_{2}\)-), 31.64 (S-CH\({}_{2}\)-CH\({}_{2}\)-), 21.63 (S-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-), 13.51 (-CH\({}_{3}\)). IR (oil): v = 2954 m, 2925 m and 2869 w (C-H stretch), 1461 m (H-C-H bend), 1060 s (C=S stretch), 884 m (H-C-S bend), 742 w (C-S stretch) cm\({}^{-1}\). HRMS (ESI\({}^{+}\)): \(m/z\): calcd for C\({}_{11}\)H\({}_{9}\)S\({}_{5}\) ([M + H]\({}^{+}\)) 311.0090; found 311.0084. _2,3-Bis_(2-cyanoethylthio)-6,7-bis_(butylthio)_tetrathiafulvalene_ (**5**): A mixture of 4,5-bis(2-cyanoethylthio)-1,3-dithiol-2-one (**4**, Sigma-Aldrich) (1 g, 3.47 mmol) and compound **3** (1.3 g, 4.16 mmol) was dried by successive evaporation of dry ACN (\(\times\)3) followed by storage in a desiccator. The residue was dissolved in trimethyl phosphite (40 mL) and the solution heated gradually to reach 110 \({}^{\circ}\)C under argon atmosphere. The solution was stirred for 2 h at 110 \({}^{\circ}\)C and subsequently allowed to cool RT. The mixture was concentrated to dryness and the residue was treated with toluene and evaporated (\(\times\)4) in order to eliminate the excess of trimethyl phosphite. The obtained residue was purified by flash chromatography on silica gel (DCM/hexane 8:2 to pure DCM) affording the desired compound **5** as a yellow solid (1.22 g, 64% yield). TLC in DCM/hexane 10:0.1, R\({}_{f}\) = 0.38. \({}^{1}\)H-NMR (400 MHz, CDCl\({}_{3}\)) \(\delta\) (ppm): 3.07 (t, \(J\) = 7.2 Hz, 4H, = C-SCH\({}_{2}\)-CH\({}_{2}\)-CN), 2.81 (t, \(J\) = 7.2 Hz, 4H, = C-SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)), 2.72 (t, \(J\) = 7.2 Hz, 4H, = C-SCH\({}_{2}\)-CH\({}_{2}\)-CN), 1.64-1.56 (m, 4H, C-SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)), 1.47-1.38 (m, 4H, C-SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)), 0.91 (t, \(J\) = 7.3 Hz, 6H, CH\({}_{3}\)). \({}^{13}\)C-NMR (100 MHz, CDCl\({}_{3}\)) \(\delta\) (ppm): 127.95 and 127.82 (S-C-S), 117.40 (CN), 114.75 (C=C), 106.38 (C=C), 36.02 (S-CH\({}_{2}\)-), 31.70 (S-CH\({}_{2}\)-CH\({}_{2}\)-),31.23 (S-CH\({}_{2}\)-CH\({}_{2}\)-CN), 21.60 (S-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-), 18.89 (S-CH\({}_{2}\)-CH\({}_{2}\)-CN), 13.57 (-CH\({}_{3}\)). IR (solid): v = 2954 m, 2924 m and 2869 m (C-H stretch), 2249 w (C\(\equiv\)N stretch), 1457 w (H-C-H bend), 1415 m-s (H-C-H bend), 889 s (H-C-S bend), 771 s (C-S stretch) cm\({}^{-1}\). HRMS (ESI\({}^{+}\)): \(m/z\): calcd for C\({}_{20}\)H\({}_{27}\)N\({}_{2}\)S\({}_{8}\) ([M + H]\({}^{+}\)) 550.9940; found 550.9956.