The synthesis of PDI-diBr and PDI-tetraBr (the polymerization initiators with two and four bromoisobutyryl groups on a PDI scaffold, respectively) was conducted in two steps. First, perylene-3,4,9,10-tetracarboxylic acid dianhydride (3.92 g, 10.0 mmol) and the aminoalcohol (100.0 mmol) were added to a round-bottom flask with 50 mL of ethylene glycol. After stirring at elevated temperature overnight, the mixture was poured into a large excess of 3% KOH solution and stood for two days. Then the sediment was collected by either filtration or centrifugation and was washed with water twice. After the freeze-drying process, the products were obtained as dark brown solids. For PDI-diBr, 2-aminaoethanol was used, and the reaction temperature was 160°C. For PDI-tetraBr, 3-aminopropane-1,2-diol was used, and the reaction temperature was 140°C. Subsequently, the PDI derivatives with hydroxyl groups (4.0 mmol) were dispersed in 100 mL of dichloromethane and 15 mL of pyridine under argon. A solution of α-bromoisobutyryl bromide (40.0 mmol) in 20 mL of dichloromethane was slowly added to the mixture. After stirring at room temperature overnight, the solution was poured into an excess amount of ethanol, and the precipitate was filtered and washed with ethanol. The dark red solid was purified by column chromatography on silica gel with a mixture of chloroform and methanol (95/5, v/v) as the eluent. PDI-diBr with dibromoisobutyryl groups, and PDI-tetraBr with tetrabromoisobutyryl groups, were obtained as dark red solids with a yield over two steps of 14% and 54%, respectively. PDI-diBr: