## 3 Materials and Methods
#### Synthesis of the Starting Substrates
\({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 12.61 (brs, 1H), 9.10 (s, 1H), 8.45-8.44 (m, 1H), 7.92 (d, \(J\) = 8.0 Hz, 1H), 7.65-7.62 (m, 2H), 7.60-7.57 (m, 2H), 7.43-7.40 (m, 1H), 7.26-7.22 (m, 2H), and 7.16-7.14 (m, 2H) ppm; \({}^{13}\)C[\({}^{1}\)H] NMR (100 MHz, DMSO-\(d_{6}\)) \(\delta\) = 145.3, 145.2, 138.7, 134.5, 130.3, 129.7, 128.3, 127.5, 127.0, 126.5, 121.9, 118.5, and 112.1 ppm. _4-{3-(1H-Benzol)[d]imidazole-yl}-1H-indol-2-yl]phenol_ (**3l**) [61]. A yield of 0.410 g (97%), 6 h, light-yellow solid. Mp. = 280 \({}^{\circ}\)C, decomposition (EtOH, lit. [61] 200 \({}^{\circ}\)C). \({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 11.87 (s, 1H), 11.62 (s, 1H), 9.67 (s, 1H), 7.86 (d, \(J\) = 7.6 Hz, 1H), 7.65-7.63 (m, 1H), 7.51-7.49 (m, 2H), 7.46-7.41 (m, 2H), 7.20-7.09 (m, 4H), and 6.85-6.82 (m, 2H) ppm; \({}^{13}\)C[\({}^{1}\)H] NMR (100 MHz, DMSO-\(d_{6}\)) \(\delta\) = 157.7, 148.5, 144.0, 138.1, 135.7, 134.5, 129.7, 128.1, 122.5, 121.8, 121.3, 120.8, 119.9, 119.7, 118.1, 115.4, 111.2, 110.9, and 102.3 ppm. _2-{2-(4-(Methoxyphenyl)-1H-indol-3-yl)-1H-benzo[d]imidazole_ isolated as a solvate with DMAC (1:0.2 DMAC) (**3m**), for no solvate [60]. A yield of 0.456 g (98%), 6 h, light beige solid. Mp. = 133-135 \({}^{\circ}\)C (DMAC/H\({}_{2}\)O, lit. for not solvate [60] 223-224 \({}^{\circ}\)C). \({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 11.93 (s, 1H), 7.84 (d, \(J\) = 7.6 Hz, 1H), 7.62-7.58 (m, 4H), 7.51 (d, \(J\) = 8.0 Hz, 1H), 7.30-7.26 (m, 2H), 7.23 (d, \(J\) = 8.0 Hz, 1H), 7.19-7.15 (m, 1H), 7.05-7.02 (m, 2H), and 3.81 (s, 3H) ppm; \({}^{13}\)C[\({}^{1}\)H] NMR (100 MHz, DMSO-\(d_{6}\)) \(\delta\) = 159.7, 147.6, 138.9, 136.9, 136.8, 135.9, 129.7, 127.6, 123.4, 122.4, 120.5, 119.4, 114.2, 111.5, 100.1, 100.0, and 55.2 ppm. _2-{(5-iodo-1H-indol-3-yl)-1H-benzo[d]imidazole_ (**3n**). A yield of 0.439 g (94%), 14 h, light beige solid. Mp. = 262-263 \({}^{\circ}\)C (EtOH). \({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 12.45 (brs, 1H), 11.74 (s, 1H), 8.90-8.89 (m, 1H), 8.13 (d, \(J\) = 2.8 Hz, 1H), 7.58-7.56 (m, 2H), 7.49 (d, \(J\) = 8.4, 1.6 Hz, 1H), 7.37 (d, \(J\) = 8.4 Hz, 1H), and 7.18-7.13 (m, 2H) ppm; \({}^{13}\)C[\({}^{1}\)H] NMR (100 MHz, DMSO-\(d_{6}\)) \(\delta\) = 148.8, 135.5, 130.1, 129.5, 127.6, 126.8, 121.2, 114.3, 105.9, and 84.2 ppm. HRMS (ESI) calcd for C\({}_{51}\)H\({}_{11}\)N [M+H]\({}^{+}\) 359.9992; found 359.982. _2-{(5-Homo-1H-indol-3-yl)-1H-benzo[d]imidazole_ (**3o**). A yield of 0.393 g (97%), 9 h, beige solid. Mp. = 261 \({}^{\circ}\)C, decomposition (petroleum ether/EtOAc). \({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 12.50 (brs, 1H), 11.77 (s, 1H), 8.70 (d, \(J\) = 2.0 Hz, 1H), 8.18 (d, \(J\) = 2.8 Hz, 1H), 7.59-7.55 (m, 2H), 7.49 (d, \(J\) = 8.4 Hz, 1H), 7.34 (dd, \(J\) = 8.4, 2.0 Hz, 1H), and 7.18-7.14 (m, 2H) ppm; \({}^{13}\)C[\({}^{1}\)H] NMR (100 MHz, DMSO-\(d_{6}\)) \(\delta\) = 148.7, 135.2, 127.3, 126.8, 124.7, 123.4, 121.2, 113.9, 112.9, and 106.1 ppm. _2-{(5-Homo-1-methyl-1H-indol-3-yl)-1H-benzo[d]imidazole_ isolated as a solvate with DMAC (1:2 DMAC) (**3q**), for no solvate [63]. A yield of 0.552 g (94%), 6.5 h, beige needles. Mp. = 123-124 \({}^{\circ}\)C (petroleum ether/EtOAc, lit. for not solvate [63] 213-215 \({}^{\circ}\)C). \({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 8.65-8.64 (m, 1H), 8.2 (s, 1H), 7.64-7.60 (m, 2H), 7.57 (d, \(J\) = 8.8 Hz, 1H), 7.43 (dd, \(J\) = 8.8, 2.0 Hz, 1H), 7.26-7.21 (m, 2H), and 3.92 (s, 3H) ppm; \({}^{13}\)Mp. = 121-122 \({}^{\circ}\)C (petroleum ether/EtOAc). \({}^{1}\)H NMR (400 MHz, DMSO-\(d_{6}\)) \(\delta\) = 12.49 (br.s, 1H), 11.60 (br.s, 1H), 8.51-8.46 (m, 1H), 8.13 (d, \(J\) = 2.8 Hz, 1H), 7.53-7.48 (m, 2H), 7.35-7.32 (m, 1H), 7.24-7.17 (m, 2H), and 7.00-6.95 (m, 1H) ppm; \({}^{13}\)C[\({}^{1}\)H] NMR (100 MHz, DMSO-\(d_{6}\)) \(\delta\) = 158.2 (d, \(J_{\rm CF}\) = 232.0 Hz), 150.9 (br.s), 136.4, 126.1, 125.0, 122.1, 121.2, 120.2, 111.8, 108.6 (d, \(J_{\rm CF}\) = 25.0 Hz), and 106.3 ppm.