1 Supporting information Synthesis, Cyclic Voltammetry and Photophysical Properties of a Bridged o-Phenylene Diamine-C 60 Dyad Michael Diekers, Andreas Hirsch, Chuping Luo, Dirk M. Guldi, Klaus Bauer and Ulrich Nickel Experimental procedures and spectroscopic data of 3, 4, and 5 Bismalonate 3 To a solution of diol 2 (50 mg, 0.15 mmol) in dry dichloromethane (50 ml), methyl malonyl chloride (42 mg, 0.31 mmol) was added under nitrogen atmosphere. The mixture was stirred at room temperature for two hours. Subsequently, the solution was washed with sodium bicarbonate solution and with water. Evaporation of the dried extract gave a slightly colored oil. Further purification was achieved by flash chromatography (toluene/triethylamine, 19/1). Yield: 3: 60 mg (0.11 mmol, 74%), colourless oil. Spectroscopic data of 3: 1 H NMR (400 MHz, CDCl 3 , 25°C): δ [ppm] = 2.39 (q,J = 6.4 Hz 4 H, CH 2 ), 3.46 (s, 4 H, CH 2 ), 3.69 (s, 6 H, CH 3 ), 4.24 (t, J = 6.4 Hz 4 H, CH 2 ), 4.63 (t, J = 6.4 Hz 4 H, CH 2 ), 7.49 (m, 4 H, CH), 8.23 (m, 4 H, CH); 13 C NMR (100.50 MHz, CDCl 3 , 25°C): δ [ppm] = 29.63 (2 C, CH 2 ), 41.40 (2 C, O=CCH 2 C=O), 52.53 (2 C, CH 3 ), 62.56 (2 C, CH 2 C=O), 71.78 (2 C, O-CH 2 ), 122.46 (4 C, CH), 125.02 (4 C, C), 125.46 (4 C, CH), 147.15 (2 C, C- O), 166.53 (2 C, C=O), 166.90 (2 C, C=O); MS (FAB): m/z = 452 (M + ); IR (KBr): ~ ν [cm -1 ] = 3057, 2955, 2846, 2801, 1735, 1590, 1496, 1438, 1413, 1385, 1150, 1022, 957, 850, 754, 686, 666; UV/Vis (CH 2 Cl 2 ): λ max (ε) [nm] = 239 (13600), 268 (6800). O-phenylene diamine-C 60 dyad 4 To a solution of C 60 (540 mg, 0.75 mmol) in dry toluene, bismalonate 3 (452 mg, 1.00 mmol), tetrabromomethane (662 mg, 2.00 mmol) and DBU (380 mg, 2.50 mmol) were added under nitrogen atmosphere. The solution was stirred at room temperature, while the progress of the reaction was monitored by TLC. After 16 hours the solution was filtered and the product was separated by flash chromatography (toluene/triethylamine, 19/1) followed by HPLC (gromsil amino phase, toluene). The product was washed with pentane and dried under vacuum. Yield: 4: 110 mg (0.09 mmol, 13%), red brownish solid. Spectroscopic data of 4: 1 H NMR (400 MHz, CDCl 3 , 25°C): δ [ppm] = 1.88 (m, 4 H, CH 2 ), 2.70 (s, 3 H, NCH 3 ), 2.80 (s, 3 H, NCH 3 ),3.15 (t, 2 H, NCH 2 ), 3.31 (m, 2 H, NCH 2 ), 3.99 (s, 3 H, OCH 3 ), 4.04 (s, 3 H, OCH 3 ), 4.18 (m, 1 H, OCH 2 ), 4.27 (m, 1 H, OCH 2 ), 4.44 (m, 1 H, OCH 2 ), 4.63 (m, 1 H, OCH 2 ), 6.92 (m, 4 H, CH); 13 C NMR (100.50 MHz, CDCl 3 , 25°C): δ [ppm] = 25.35 (1 C, CH 2 ), 25.55 (1 C, CH 2 ) 39.36 (1 C, NCH 3 ), 40.08 (1 C, NCH 3 ), 50.22 (1 C, NCH 2 ), 50.44 (1 C, NCH 2 ), 51.37 (1 C, Bk-C), 53.85 (1 C, bridgehead-C), 53.92 (1 C, OCH 3 ), 53.98 (1 C, OCH 3 ), 65.87 (1 C, OCH 2 ), 66.00 (1 C, OCH 2 ), 70.35 (1 C, sp 3 -C 60 -C), 71.50 (1 C, sp 3 -C 60 -C), 71.61 (2 C, sp 3 -C 60 -C), 119.44 (1 C, CH), 120.43 (1 C, CH), 121.85 (1 C, CH), 122.60 (1 C, CH), 138.64, 138.90, 139.63, 140.71, 141.27, 141.51, 141.66, 141.86, 141.93, 142.08, 142.33, 142.53, 143.06, 143.26, 143.45, 143.56, 143.70, 143.81, 143.85, 143.94, 144.03, 144.09, 144.31, 144.47, 144.60, 144.69, 144.76, 144.87,