# 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
IR (solid): v = 2956 m, 2912 m and 2854 m (C-H stretch), 1704 s (C=O stretch), 1465 m (H-C-H bend), 1438 m-s (O-H bend), 1294 m (C-O stretch), 947 m, broad (O-H bend), 887 m (H-C-S bend), 788 m-s, 772 m-s and 740 m-s (C-S stretch) cm\({}^{-1}\). HRMS (ESI): \(m/z\): calcd. for C\({}_{21}\)H\({}_{31}\)O\({}_{2}\)S\({}_{8}\) 571.0095; found 571.0093. N-[\(N^{\prime}\)-(_Tetr_-butoxycarbonyl)glyglyglyglyglyglygly]-L-threonine (**13**): The \(N\)-protected tripeptide Boc-(Gly)\({}_{3}\)-OH (**9**, Bachem) (1.05 g, 3.54 mmol) along with 4-nitrophenol (**10**, Fluka) (0.59 g, 4.25 mmol) were dissolved in anhydrous pyridine (15 mL) under argon and the solution was cooled at 0 \({}^{\circ}\)C. Then, 1,3-dicyclohexylcarbodiimide (DCC) (0.88 g, 4.25 mmol) was added under argon and the reaction was stirred at 0 \({}^{\circ}\)C for 30 min and then at RT overnight. After this time, the precipitate was filtered out and the solvent was removed under vacuum. The obtained residue was dissolved in toluene and concentrated to dryness under reduced pressure (\(\times\)3). The resulting 4-nitrophenyl ester **11** was used in the next step without further purification. The activated acid and (2\(R\), 3_R_)-2-aminobutane-1,3-diol (**12**, L-threninol, Sigma-Aldrich) (0.41 g, 3.89 mmol) were dissolved in anhydrous DMF (15 mL) under argon and stirred at RT for 3 h. After this time, the solvent was removed under reduced pressure and the residue was dissolved in toluene and concentrated to dryness (\(\times\)3). The obtained residue was purified by flash chromatography on silica gel (crude adsorbed onto the silica, DCM/MeOH 100:5\(\rightarrow\)100:15) affording the desired compound **13** as a white solid (1.13 g, 87%). TLC in DCM/MeOH 100:10, R\({}_{f}\) = 0.35. 1\({}^{1}\)H-NMR (400 MHz, DMSO-d\({}_{6}\)) 8 (ppm): 8.07-8.01 (m, 2H, NH), 7.25 (d, \(J\) = 8.0 Hz, 1H, NH), 6.95 (t, \(J\) = 6.0 Hz, 1H, NH), 4.52-4.50 (br, 2H, OH), 3.85-3.83 (m, 1H, OH-CH-CH\({}_{3}\)), 3.71-3.68 (m, 4H, NH-CH\({}_{2}\)-CO), 3.62-3.56 (m, 2H, NH-CH-CH\({}_{2}\)), 3.56 (d, \(J\) = 8.0 Hz, 2H, NH-CH\({}_{2}\)-CO), 3.44-3.37 (m, 1H, OH-CH\({}_{A}\)H\({}_{B}\)-CH), 3.31-3.26 (m, 1H, OH-CH\({}_{A}\)H\({}_{B}\)-CH), 1.35 (s, 9H, (CH\({}_{3}\))\({}_{3}\)-C), 0.95 (d, \(J\) = 6.4 Hz, 3H, CH\({}_{3}\)-CH-CH). 13C-NMR (100 MHz, DMSO-d\({}_{6}\)) \(\delta\) (ppm): 170.58 (NH-CO), 169.67 (NH-CO), 169.37 (NH-CO), 156.50 (O-CO-NH), 78.83 (CH\({}_{3}\)-C), 64.88 (CH\({}_{3}\)-CH), 61.12 (OH-CH\({}_{2}\)-CH), 56.43 (NH-CH-CH), 43.99 (NH-CH\({}_{2}\)-CO), 42.77 (NH-CH\({}_{2}\)-CO), 42.70 (NH-CH\({}_{2}\)-CO), 28.87 (CH\({}_{3}\)-C), 20.73 (CH\({}_{3}\)-CH). IR (solid): \(\
u\) = 3428 w, broad, 3294 m, broad and 3094 w, broad (N-H and O-H stretch), 2963 w and 2929 w (C-H stretch), 1683 m and 1632 s (C=O stretch), 1525 s (N-H bending), 1481 w-1394 w (C-H bend), 1279 m, 1244 s, 1156 m, 1123 w, 1102 w, 1076 m, 1048 m and 1025 m (C-O stretch or C-N stretch), 947 m and 857 m (C-H bend), 654 m, broad (N-H out of plane bend). HRMS (ESI\({}^{+}\)): \(m/z\): calcd. for C\({}_{15}\)H\({}_{29}\)N\({}_{4}\)O\({}_{7}\)([M + H]\({}^{+}\)) 377.2036 found 377.2031; \(m/z\): calcd. for C\({}_{15}\)H\({}_{28}\)N\({}_{4}\)NaO\({}_{7}\)([M + Na]\({}^{+}\)) 399.1856 found 399.1856. _L-Threninol-(Gly)\({}_{3}\)-TTF derivative_ (**14**): Compound **13** (0.87 g, 2,32 mmol) was dissolved in DCM (10 mL) and TFA (1 mL) was added slowly at RT. Stirring was continued until TLC showed no remaining starting material (ca. 1-1.5 h) and the mixture was concentrated to dryness under reduced pressure. The obtained residue was dissolved in toluene and concentrated to dryness under reduced pressure. This process was repeated three times to remove traces of TFA to yield the TFA salt of the deprotected amino compound (colorless oil). This crude TFA salt was dried in vacuo and used in the next step without purification.