## 2 Materials and Methods
\({}^{1}\)H-NMR (400 MHz, CDCl\({}_{3}\)) ppm, \(\delta\): 7.35-7.29 (m, 6 H), 7.21-7.18 (m, 4H), 7.15 (d, 8.6 Hz, 4H), 6.64 (d, 8.6 Hz, 4H). \({}^{13}\)C-NMR (100.61 MHz, CDCl\({}_{3}\)) ppm, \(\delta\): 167.61, 149.31, 132.33, 131.23, 131.18, 131.05, 130.98, 130.89, 129.39, 128.93, 123.38, 111.05, 87.40. **Synthesis of 3,4-Bis-4-([5-methyl)]-1,6 ieryl-2,5-diphenylcyclopentadiene (5T). ** A solution of 5-Methylthiophene-2-boronic acid pinnocl ester **4T** (0.58 mg, 2.59 mmol), **3** (364 mg, 0.53 mmol), [1,1\({}^{\prime}\)-Bis(diphenylphosphino)],ferrocene]dichloropalladium(II)\({}^{\prime}\)CH\({}_{2}\)Cl\({}_{2}\) (45 mg, 0.053 mmol, 0.1 eq), K\({}_{2}\)CO\({}_{3}\) (366 mg, 2.65 mmol, 5 eq) in dry toluene (20 mL), and dry methanol (20 mL) under nitrogen atmosphere was stirred at reflux for 18 h. At room temperature, H\({}_{2}\)O was added, and the mixture was extracted with CH\({}_{2}\)Cl\({}_{2}\) (3 \(\times\) 100 mL). Organic phase was dried with Na\({}_{2}\)SO\({}_{4}\). The crude of the reaction was a red oil. Column chromatography on silica gel and 9/1 hexane: ethyl acetate as mobile phase afforded pure product as a brown solid (194.70 mg, 64%). \({}^{1}\)H-NMR (400 MHz, CDCl\({}_{3}\)) ppm, \(\delta\): 7.39 (d, \(J\) = 8.6 Hz, 4H), 7.30-7.27 (m,10H), 7.12 (d, \(J\) = 3.4, 2H), 6.95 (d, \(J\) = 8.6 Hz, 4H), 6.73 (d, \(J\) = 3.4, 2H), 2.50 (s, 6H). \({}^{13}\)C-NMR (100.61 MHz, CDCl\({}_{3}\)) ppm, _s_: 200.03, 153.71, 141.20, 140.27, 134.80, 131.46, 130.88, 130.21, 130.15, 128.13, 127.51, 126.42, 125.46, 124.67, 123.49, 15.53. **Synthesis of 3,4-Bis-4-[(4-fluoro)-phenyl]-2,5-diphenylcyclopentatione (5F). ** A solution of 4-Fluorophenylboronic acid, pinacol ester **4F** (573.31 mg, 2.58 mmol, 4 eq), 3 (350 mg, 0.645 mmol), [1,1\({}^{\prime}\)-Bis(diphenylphosphino)ferroceen]dichloroppalladium(II)\({}^{\prime}\)CH\({}_{2}\)Cl\({}_{2}\) (52.66 mg, 0.0645 mmol, 0.1 eq), K\({}_{2}\)CO\({}_{3}\) (445.69 mg, 3.225 mmol, 5 eq) in dry toluene (20 mL), and dry methanol (20 mL) under nitrogen atmosphere was stirred at reflux for 18 h. At room temperature, H\({}_{2}\)O was added, and the mixture was extracted with CH\({}_{2}\)Cl\({}_{2}\) (3 \(\times\) 100 mL). Organic phase was dried with Na\({}_{2}\)SO\({}_{4}\). The crude of the reaction was a red oil. Column chromatography on silica gel and 9.3/0.7 hexane: ethyl acetate as mobile phase afforded pure product as a brown solid (269 mg, 72%). \({}^{1}\)H-NMR (400 MHz, CDCl\({}_{3}\)) ppm, _s_: 7.58-7.52 (m, 4H), 7.41 (d, \(J\) = 8.6 Hz, 4H), 7.32-7.24 (m, 10H), 7.12 (t, \(J\) = 8.6 Hz, 4H), 7.05 (d, \(J\) = 8.6 Hz, 4H). \({}^{13}\)C-NMR (100.61 MHz, CDCl\({}_{3}\)) ppm, _s_: 200.05, 163.90, 161.44, 153.76, 140.07, 136.22, 131.96, 130.77, 130.21, 130.10, 128.57, 128.49, 128.14, 127.58, 126.36, 125.65, 115.86, 115.64. **Synthesis of 3,4-Bis-4-[(5-methyl)-tiofenyl]-phenyl-2,5-diphenyl-1,1\({}^{\prime}\)-bis-methylmalo nyl-fulvene (5 mT, 2 nd procedure). ** To an ice-cooled solution of 3,4-Bis-4-[(5-methyl)-tiofenyl]-2,5-diphenylcyclopentadienone **5T** (0.374 g, 0.65 mmol) and dimethyl malonate **4m** (343.49 mg, 0.3 mL, 2.6 mmol, 4 eq) in 20 mL of dichloromethane (dry) under argon atmosphere, TiCl\({}_{4}\) (5 eq, 3.25 mmol, 616.46 mg, 0.356 mL) over 5 min and pyridine (24 eq, 1.233 g, 15.6 mmol, 1.2 mL) were added dropwise. The reaction mixture was allowed to warm at room temperature and stirred overnight. A total of 50 mL of dichloromethane and 50 mL of HCl 0.1 M were added. The mixture was extracted with dichloromethane (3 \(\times\) 100 mL) and dried with Na\({}_{2}\)SO\({}_{4}\). Column chromatography on silica gel and hexane/ethyl acetate 9:1 as the mobile phase afforded pure product as a light-brown solid (300 mg, 1.027 mmol, 67%). \({}^{1}\)H-NMR (400 MHz, CDCl\({}_{3}\)) ppm, _s_: 7.30-7.15 (m, 14 H), 7.03 (d, \(J\) = 3.4, 2H), 6.72 (d, \(J\) = 8.6 Hz, 4H), 6.67 (dd, \(J\) = 1.3, 4.1, 2H), 3.07 (s, 6H), 2.48 (s, 6H).