Compound 0

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Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

Synthesis of P3: a 25 mL round bottom flask was charged with B1 (50 mg, 0.176 mmol), and 1,8-naphthalic anhydride (209 mg, 1.06 mmol). To this was added 3 g of imidazole and 0.75 mL of dry toluene. The mixture was heated to 140 ^oC for 16 hr then cooled slightly and partitioned between CH₂Cl₂ (50 mL) and 2 M HCl (50 mL). The organic layer was dried over MgSO₄ then concentrated in vacuo. The residue was purified by column chromatography (hexanes/CH₂Cl₂) to afford the product as an off-while solid (62 mg, 55%). ¹H NMR (500 MHz, CDCl₃) δ 8.61 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (dd, J = 7.2, 1.2 Hz, 2H), 8.26 (dd, J = 8.4, 1.1 Hz, 1H), 8.09 (dd, J = 7.2, 1.2 Hz, 2H), 8.01 (ddd, J = 8.3, 2.5, 1.2 Hz, 4H), 7.78 (dd, J = 8.2, 7.3 Hz, 1H), 7.54 (dd, J = 8.2, 7.2 Hz, 2H), 7.51 – 7.48 (m, 2H), 7.43 (dd, J = 8.2, 7.1 Hz, 2H), 7.13 (t, J = 7.7 Hz, 2H), 7.03 – 7.00 (m, 1H), 6.92 (dd, J = 8.0, 1.0 Hz, 2H), 5.61 (s, 1H), 5.06 (s, 1H). ¹³C NMR (126 MHz, CDCl₃) δ 163.44, 163.20, 147.07, 145.04, 143.29, 141.69, 134.69, 133.55, 133.38, 131.23, 131.18, 131.11, 130.96, 130.40, 127.93, 126.97, 126.64, 126.61, 125.72, 125.33, 125.22, 123.82, 123.32, 122.55, 122.40, 116.46, 77.27, 77.02, 76.76, 53.43, 46.72. MS (MALDI-TOF): m/z calcd for C₄₄H₂₄N₂O₄, [M]^- 644.17, found 644.13.

A flame dried 5 mL microwave vial was charged with P3 (42 mg, 0.0651 mmol) and PMI-c15 (Feiler L, Langhals H, Polborn K. Synthesis of perylene-3,4-dicarboximides — Novel highly photostable fluorescent dyes. Liebigs Annalen, 7, 1229-1244 (1995)) (208 mg, 0.391 mmol). In a glovebox, the mixture was suspended in 3 mL of dry toluene. A second flame dried 20 mL microwave vial was charged with potassium tert-butoxide (87.6 mg, 0.781 mmol) and 1,5-diazabicyclo(4.3.0)non-5-ene (0.145 mL, 1.17 mmol) in 3 mL of dry toluene. Both flasks were sealed and removed from the glovebox. The two flasks were heated to 100 ^oC to dissolve the reagents, then the P2 and PMI mixture were injected over ~5 minutes, under N₂, into the vial containing the bases. The reaction vial was then heated to 130 ^oC for 3 hr, turning blue and precipitating a solid on the side of the flask. After cooling, the mixture was partitioned between CH₂Cl₂ (50 mL) and 1 M HCl (50 mL). The aqueous layer was extracted twice with CH₂Cl₂ (20 mL) and the combined organic layers were concentrated in vacuo. The residue was purified by size exclusion chromatography (Bio-Rad Bio-Beads, S-X1, CH₂Cl₂) followed by silica gel chromatography (hexanes/CH₂Cl₂) to afford the product as a dark blue solid (20 mg, 18 %). Spectroscopic samples were further purified by HPLC (HP Agilent 1100). ¹H NMR (500 MHz, C₂D₂Cl₄) δ 8.85 – 8.59 (m, 8H), 8.49 (d, J = 7.6 Hz, 2H), 8.33 (d, J = 7.6 Hz, 1H), 8.27 – 8.16 (m, 8H) 8.05 – 8.01 (m, 2H), 7.59 – 7.42 (m, 8H), 7.26 – 7.11 (m, 4H), 7.01 (d, J = 7.9 Hz, 1H), 5.65 (s, 1H), 5.23 (m, 2H), 5.12 (s, 1H), 2.33 (m, 12H), 1.99 (m, 8H), 1.36 (m, 28H), 0.95 (m, 12H). ¹³C NMR was not obtained due to sparing solubility. MS (MALDI-TOF): m/z calcd for C₁₁₈H₉₈N₄O₈, [M]^- 1699.74, found 1699.72.