# 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\({}^{\prime}\),5,5\({}^{\prime}\)-Tris(butylsulfanyl)-2,2\({}^{\prime}\)-bis-1,3-dithiol-4-yl]sulfanyl]propanoic acid_ (**8**, 0.95 g, 1.66 mmol) along with \(N\)-hydroxysuccinide (NHS) (Sigma-Aldrich) (0.21 g, 1.83 mmol) were dissolved in anhydrous THF (40 mL) under argon and the solution was cooled at 0\({}^{\circ}\)C. Then, DCC (0.38 g, 1.83 mmol) was added under argon and the reaction was stirred at 0 \({}^{\circ}\)C for 30 min and at RT overnight. The precipitate was filtered out and the solvent was removed under reduced pressure. The resulting \(N\)-hydroxysuccinimide ester was used in the next step without further purification. The active ester was dissolved in anhydrous DMF (30 mL). The TFA salt of the deprotected amino compound was dissolved in DMF (30 mL) and \(N\),\(N\)-disopropylethylamine (DIEA) (405 \(\mu\)L, 2.32 mmol) was added. Then, the solution of the active ester was added under argon and the mixture was allowed to react at RT for 30 min. The solvent was removed under reduced pressure and the residue was dissolved in toluene and concentrated to dryness (\(\times\)3). The crude compound was washed with hexane (5 \(\times\) 70 mL) and with diethyl ether (5 \(\times\) 70 mL). The residue was dissolved in DCM (300 mL) and the organic phase was washed with 5% aqueous NaHCO\({}_{3}\) (2 \(\times\) 75 mL) and saturated aqueous NaCl (75 mL), dried over anhydrous MgSO\({}_{4}\), and concentrated to dryness under reduced pressure. The crude residue was purified by chromatography on silica gel (DCM/MeOH 100:0.5\(\rightarrow\)90:10) obtaining a reddish solid (868 mg, 62%). TLC (DCM/MeOH 100:1) R\({}_{f}\) = 0.10. 1\({}^{1}\)H-NMR (400 MHz, CD\({}_{3}\)OD) 8 (ppm): 7.83-7.52 (NH zone), 3.98-3.95 (m, 1H, OH-CH-CH\({}_{3}\)), 3.91-3.69 (m, 6H, NH-CH\({}_{2}\)-CO), 3.82-3.79 (m, 1H, NH-CH-CH\({}_{2}\)), 3.66-3.62 (m, 1H, OH-CH\({}_{A}\)H\({}_{B}\)-CH), 3.60-3.55 (m, 1H, OH-CH\({}_{A}\)H\({}_{B}\)-CH), 3.09 (t, \(J\) = 7.2 Hz, 2H, SCH\({}_{2}\)-CH\({}_{2}\)-CONH), 2.87-2.81 (m, 6H, SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)), 2.64 (t, \(J\) = 7.2 Hz, 2H, SCH\({}_{2}\)-CH\({}_{2}\)-CONH), 1.64-1.56 (m, 6H, C-SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)), 1.49-1.40 (m, 6H, C-SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)), 1.43 (d, \(J\) = 6.4 Hz, 3H, CH\({}_{3}\)-CH-CH), 0.92 (t, 9H, \(J\) = 7.2 Hz, SCH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)). 13C-NMR (100 MHz, CD\({}_{3}\)OD) \(\delta\) (ppm): 172.71, 171.21, 170.82 and 170.44 (NH-CO), 129.50, 127.78, 127.10 and 126.18 (-CH\({}_{2}\)-S-C-S), 110.15 and 109.49 (S\({}_{2}\)=CS\({}_{2}\)), 65.80 (CH\({}_{3}\)-CH), 61.35 (OH-CH\({}_{2}\)-CH), 56.34 (NH-CH-CH), 42.49, 42.43 and 42.17 (NH-CH\({}_{2}\)-CO), 35.52, 35.45, 35.40 and 35.38 (S-CH\({}_{2}\)- and SCH\({}_{2}\)-CH\({}_{2}\)-CONH), 31.59, 31.56 and 31.55(S-CH\({}_{2}\)-CH\({}_{2}\)), 31.02 (SCH\({}_{2}\)-CH\({}_{2}\)-CONH), 21.16 and 21.14 (S-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-), 18.92 (CH\({}_{3}\)-CH), 12.54 and 12.51 (S-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{2}\)-CH\({}_{3}\)). IR (solid): v = 3280 m, broad and 3086 w, broad (O-H and N-H stretch), 2955 m-w, 2926 m-w and 2869 w (C-H stretch), 1642 s (C=O stretch), 1553 m-s (N-H bend), 1456 m-w, 1417 m-w and 1376 m-w (C-H bend or O-H bend or H-C-H bend), 1249 m, 1099 m and 1028 m (C-O stretch and N-H stretch), 886 w (H-C-S bend or C-H bend), 771 m (C-S stretch), 684 m, broad (N-H out of plane). HRMS (ESI\({}^{+}\)): \(m/z\): calcd for C\({}_{31}\)H\({}_{52}\)N\({}_{4}\)O\({}_{2}\)S\({}_{8}\) ([M + H]\({}^{+}\)) 831.1574 found 831.1613; \(m/z\): calcd for C\({}_{31}\)H\({}_{52}\)N\({}_{4}\)NaO\({}_{2}\)S\({}_{8}\) ([M + Na]\({}^{+}\)) 853.1394 found 853.1416.