## 2 Materials and Methods
### Synthesis of 3-5-(Bromothiophen-2-yl)-2-(4-Fluorobenzoyl) Acrylonitrile (2)  
3-5-(bromothiophen-2-yl)-2-(4-fluorobenzoyl) acrylonitrile was synthesized by consulting the reported literature [35]. In a round bottom flask, 5-bromo-2-thiophen-carboxaldehyde de (1.582 g, 8.28 mmol) and 4-fluorobenzoylacetonitrile (1.35 g, 8.28 mmol, 1 equiv.) were stirred in 50 mL degassed ethanol at room temperature under argon atmosphere for 1 h. Thereafter, potassium tertiary butoxide, t-BuOK (0.41 g, 3.72 mmol, 0.45 equiv.) in 10 mL of ethanol was dropped in the reaction mixture and further subjected to stirring for 5 h at 298 K. Obtained yellow precipitates were filtered out, washed with deionized (DI) water and methanol. The purification of the crude product was carried out with the help of flash column chromatography using dichloromethane and hexane as eluents (DCM: hexane, 1:2 _v/v_). The resulted dried solid was recrystallized with dichloromethane and ethyl acetate (DCM: EtOAc, 1:10 _v/v_) to obtain intermediate (**2**) as a light yellow crystal (yield 76.57%, 2.13 g) \({}^{1}\)H NMR (500 MHz, CDCl\({}_{3}\), ppm) \(\delta\): 8.18 (s, 1H), 7.95 (dd, J = 8.7 Hz, 5.2 Hz, 2H), 7.56 (d, J = 4.0 Hz, 1H), 7.2 (d, J = 4.0 Hz, 1H), 7.18 (t, J = 8.6 Hz, 2H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\), ppm) \(\delta\): 186.39, 166.93, 164.89, 147.03, 138.76, 138.11, 131.98, 131.90, 131.77, 125.21, 117.57, 116.13, 115.95, 105.56. MS: m/z calc. for [C\({}_{14}\)H\({}_{7}\)BrFNOS + H]\({}^{+}\): 337.18; found: 337.98.  
Synthesis of 2-(4-Fluorobenzoyl)-3-(5\({}^{\circ}\)-hexyl-[2,2\({}^{\prime}\):5\({}^{\prime}\),2\({}^{\prime\prime}\)-Terthiophene]-5-yl) Acrylonitrile, (H3T-4-FOP)  
5\({}^{\prime}\)-hexyl-2,2\({}^{\prime}\)-bithiophene-5-boronic acid pinocal ester (0.942 g, 2.50 mmol), 3-5(bromo thiophen-2-yl)-2-(4-fluorobenzoyl) acrylonitrile (0.504 g, 3.75 mmol, 1.5 equiv.) and 5 mol% Pd(PPh\({}_{3}\))\({}_{4}\) were stirred in toluene (anhydrodus, 30 mL). After 30 min, 2 M potassium carbonate (K\({}_{2}\)CO\({}_{3}\)) in 5 mL of water was introduced in the reaction and refluxed at 110 \({}^{\circ}\)C for 24 h. Afterwards, the reaction mixture was allowed to cool at room temperature, washed with DI water and brine. The resulting organic phase was extracted with DCM, dried over MgSO\({}_{4}\) and evaporated under vacuum conditions. The crude product was further purified by flash column chromatography with dichloromethane and hexane as eluents (DCM: hexane, 1:5 _v/v_) and dried in an oven. Thereafter, recrystallized twice with (DCM: EtOAc, 1:10 _v/v_) to obtain a bright red crystal (yield 63.21% 0.758 g). \({}^{1}\)H NMR (500 MHz, CDCl\({}_{3}\), ppm) \(\delta\): 8.25 (s, 1H), 7.95 (dd, J = 5.2 Hz, 3.9 Hz, 2H), 7.70 (d, J = 4.3 Hz, 1H), 7.31 (d, J = 2.3 Hz, 1H), 7.23 (d, J = 4.1 Hz, 1H), 7.18 (t, J = 8.6 Hz, 2H), 7.05 (dd, J = 6.0 Hz, 3.8 Hz, 2H), 6.70 (d, J = 3.6 Hz, 1H), 6.79 (t, J = 7.6 Hz, 2H), 1.63 (m, 4H), 1.33 (m, 4H), 0.88 (t, J = 6.8 Hz, 3H). \({}^{13}\)C NMR (100 MHz CDCl\({}_{3}\), ppm) \(\delta\): 186.68, 166.73, 164.71, 148.48, 147.50, 147.20, 140.84, 140.47, 134.62, 133.75, 133.45, 131.86, 131.69, 127.75, 125.27, 124.61, 124.33, 124.17, 118.17, 115.99, 115.81, 103.51, 31.64, 31.62, 30.32, 28.82, 22.64, 14.15. MS: m/z calc. for [C\({}_{28}\)H\({}_{24}\)FNOS\({}_{3}\) + H]\({}^{+}\): 505.69; found: 506.45. Elemental analysis for C\({}_{28}\)H\({}_{24}\)FNOS\({}_{3}\), calculated: C, 66.50; H, 4.78; F, 3.76; N, 2.77; O, 3.16; S, 19.02. Found: C, 66.67; H, 4.73; F, 3.72; N, 2.79; O, 3.15; S, 18.89.