Synthesis of porphyrin acrylate (PorAc)

The procedure was similar to the synthesis of Azo-C₃–OH, except that the Azo-OH was replaced in this route by Por-OH with the yield of 89% (1.37 g). ¹H-NMR (500 MHz, CDCl₃): δ (ppm) − 2.34 (s, 2H, NH pyrrole), 2.23 (q, 2H, CH₂CH₂CH₂), 4.03 (t, 2H, CH₂CH₂O–C=O), 4.4 (t, 2H, Ar–O–CH₂CH₂), 7.07–7.25 (m, 8H), 7.43–7.51 (m, 3H), 7.79–7.88 (m, 3H), 8.06–8.16 (m, 5H), 8.23–8.32 (m, 6H), 8.43–8.51 (m, 4H), 8.55–8.61 (m, 2H), 8.76–8.82 (m, 2H).

Acryloyl chloride (0.1 mL, 1.2 mmol) was dissolved in dry THF (5 mL) and added dropwise to the stirring mixture of Et₃N (0.17 mL, 1.2 mmol) and Por-C₃–OH (0.1 g, 0.12 mmol) in dry THF (10 mL) over 1 h at 0 °C. The reaction mixture was stirred overnight at 25 °C, and then, the solvent was evaporated under reduced pressure. In the next step, distilled water (20 mL) was added into the residue and the product was extracted three times with DCM (20 mL). After removing DCM, the crude product was purified by using a silica gel column with DCM, as the eluent, to obtain 90 mg of PorAc monomer with 85% yield. ¹H-NMR (500 MHz, CDCl₃): δ (ppm) − 2.30 (s, 2H, NH pyrrole), 2.37 (q, 2H, CH₂CH₂CH₂), 4.36 (t, 2H, CH₂CH₂O–C=O), 4.54 (t, 2H, Ar–O–CH₂CH₂), 5.90 (d, 1H, (C=O)–CH=CH₂), 6.23 (dd, 1H, (C=O)–CH=CH₂), 6.51 (d, 1H, (C=O)–CH=CH₂), 7.09–7.28 (m, 8H), 7.46–7.53 (m, 3H), 7.80–7.90 (m, 3H), 8.10–8.17 (m, 5H), 8.24–8.35 (m, 6H), 8.46–8.54 (m, 4H), 8.58–8.64 (m, 2H), 8.79–8.85 (m, 2H).