Beilstein J. Org. Chem. 2020, 16, 763–777.
(td, J = 7.5, 1.2 Hz, 3H, triptycene-H), 4.94–4.87 (m, 4H, ture for three hours. The progress of the reaction was moni-
hexyl-CH2), 2.54 (dt, J = 15.2, 7.6 Hz, 4H, hexyl-CH2), 1.85 tored by TLC and once all starting material had been consumed
(dt, J = 15.2, 7.6 Hz, 4H, hexyl-CH2), 1.54 (d, J = 7.6 Hz, 4H, the reaction mixture was filtered through silica gel using
hexyl-CH2), 1.43 (dd, J = 7.6, 2.5 Hz, 4H, hexyl-CH2), 1.40 CH2Cl2 as eluent. The solvents were removed in vacuo and the
(dd, 21H, TIPS-CH3), 0.95 ppm (t, J = 7.6 Hz, 6H, hexyl-CH3); crude product was purified by recrystallisation from CHCl3/
13C NMR (151 MHz, CDCl3) δ 151.9, 150.8, 150.1, 149.3, CH3OH. The product was obtained as purple crystals (19 mg,
144.7, 144.1, 142.9, 134.4, 132.8, 132.3, 131.3, 130.2, 128.8, 15%). Mp 298 °C (dec.). Rf = 0.75 (SiO2, CH2Cl2/n-hexane,
127.7, 126.7, 126.2, 123.0, 122.8, 122.1, 101.6, 98.1, 95.9, 94.4, 3:1, v/v); 1H NMR (400 MHz, CDCl3) δ 9.63 (d, J = 4.6 Hz,
89.9, 54.4, 53.9, 39.1, 35.8, 32.1, 30.5, 29.8, 22.9, 19.0, 14.3, 4H, Hβ), 8.85 (s, 2H, phenyl-H), 8.77 (d, J = 4.6 Hz, 4H, Hβ),
11.7 ppm; IR (neat)/cm−1) ν̃: 2921 (m), 2851 (m), 1451 (m), 8.52 (d, J = 7.7 Hz, 2H, phenyl-H), 8.34 (d, J = 7.7 Hz, 2H,
1305 (m), 1211 (m), 1072 (m), 1008 (s), 939 (m), 787 (s), 750 phenyl-H), 7.88 (t, J = 7.7 Hz, 2H, phenyl-H), 4.01 (s, 6H,
(s), 708 (s), 639 (s); UV–vis (CHCl3) λmax [nm] (log ε): 430 ester-CH3), −2.77 ppm (s, 2H, NH); 13C NMR (101 MHz,
(5.84), 563 (4.30), 608 (4.35); HRMS–MALDI (m/z): [M]+ CDCl3) δ 167.3, 141.8, 138.5, 134.9, 129.5, 129.2, 127.2,
calcd for C71H72N4SiZn, 1072.4818; found, 1072.4800.
120.2, 104.2, 52.6; IR (neat)/cm−1) ν̃: 2923 (m), 2853 (w), 1726
(s), 1580 (w), 1463 (w), 1436 (m), 1286 (m), 1241 (s), 1190
(m), 1105 (m), 961 (m), 791 (s), 746 (s), 728 (s), 629 (m);
UV–vis (CHCl3): λmax [nm] (log ε) = 424 (5.51), 523 (4.21),
558 (3.00), 603 (3.72), 660 (3.67); HRMS–MALDI (m/z): [M]+
calcd for C36H24N4O4Br2, 734.0164; found, 734.0186.
Synthesis of 9-[(10,20-dihexyl-15-phenylporphyri-
nato-5-yl)ethynyl]zinc(II)-10-[(10,20-dihexyl-15-
phenylporphyrinato-5-yl)ethynyl]nickel(II)-triptycene
(16)
Porphyrin 15 (15.6 mg, 2.2 μmol) and the triptycene–porphyrin
14 (14 mg, 15 μmol) were placed in an oven dried Schlenk flask Synthesis of [5,15-bis(3'-methoxycarbonylphenyl)-
and heated under vacuum. The flask was purged with argon and 10,20-dibromoporphyrinato]zinc(II) (17c)
anhydrous THF/NEt3 (1 mL:0.33 mL) were added by syringe. Synthesized from free base porphyrin 17b (60 mg,
Argon was bubbled through the solution for five minutes. 0.081 mmol), Zn(II)(OAc)2·2H2O (89 mg, 0.41 mmol in CHCl3
PdCl2(PPh3)2 (1.5 mg, 2 μmol) and CuI (1 mg, 4 μmol) were and MeOH (50 mL:15 mL) by stirring the porphyrin solution at
added and the reaction mixture was stirred at 70 °C for 18 hours room temperature for four hours. The reaction process was
and then diluted with CH2Cl2 (10 mL) before removal of sol- monitored by TLC and once all the starting material was con-
vents in vacuo. The crude material was purified by filtration sumed the reaction mixture was washed with NaHCO3, dried
with a silica gel column using 2:1: CH2Cl2/n-hexane. Recrystal- over MgSO4 and filtered through silica gel using CH2Cl2 as the
lization (CHCl3/n-hexane) yielded purple crystals (2 mg, 8%). eluent. Purple crystals were obtained (60 mg, 92%). Mp 307 °C.
Mp 335–338 °C. Rf = 0.7 (SiO2, CH2Cl2/n-hexane, 2:1, v/v); Rf = 0.22 (SiO2, CH2Cl2/n-hexane, 3:1, v/v); 1H NMR
1H NMR (600 MHz, CDCl3) δ 10.23 (d, J = 4.3 Hz, 4H, Hβ), (400 MHz, CDCl3) δ 9.65 (d, J = 4.7 Hz, 4H, Hβ), 8.79 (s, 2H,
9.70 (d, J = 4.3 Hz, 4H, Hβ), 9.49 (d, J = 4.3 Hz, 4H, Hβ), 8.95 phenyl-H), 8.76 (d, J = 4.7 Hz, 4H, Hβ), 8.45 (d, J = 7.7 Hz,
(d, J = 4.4 Hz, 4H, Hβ), 8.70 (dd, J = 5.2, 3.3 Hz, 6H, trip- 2H, phenyl-H), 8.34 (d, J = 7.7 Hz, 2H, phenyl-H), 7.83 (t, J =
tycene-H), 8.23 (d, J = 6.7 Hz, 4H, phenyl-H), 7.78 (t, J = 7.7 Hz, 2H, phenyl-H), 3.98 ppm (d, 6H, ester-CH3); 13C NMR
6.7 Hz, 6H, phenyl-H), 7.48 (dd, J = 5.6, 2.4 Hz, 6H, trip- (101 MHz, CDCl3) δ 167.7, 150.6, 150.3, 143.0, 138.5, 134.9,
tycene-H), 5.00–4.95 (m, 8H, hexyl-CH2), 2.63–2.55 (m, 8H, 133.3, 133.1, 128.9, 128.5, 126.8, 120.5, 105.1, 52.5; IR (neat)/
hexyl-CH2), 1.92–1.84 (m, 8H, hexyl-CH2), 1.60–1.55 (m, 8H, cm−1) ν̃: 1697 (m), 1430 (w), 1286 (m), 1227 (m), 1022 (m),
hexyl-CH2), 1.48–1.41 (m, 8H, hexyl-CH2), 0.97 (t, J = 7.3 Hz, 997 (s), 791 (s), 755 (s), 732 (s), 696 (m); UV–vis (CHCl3)
12H); 13C NMR (101 MHz, CDCl3) δ 167.7, 150.6, 150.3, λmax [nm] (log ε): 425 (5.68), 556 (4.34), 596 (3.82);
143.0, 138.5, 134.9, 133.3, 133.1, 128.9, 128.5, 126.8, 120.5, HRMS–MALDI (m/z): [M]+ calcd for C36H22N4O4Br2Zn,
105.1, 52.5; UV–vis (CHCl3) λmax [nm] (log ε): 433 (5.77), 563 795.9299; found, 795.9333.
(4.32), 609 (4.31); HRMS–MALDI (m/z): [M]+ calcd for
C100H90N8NiZn, 1524.5933; found, 1524.5970.
Synthesis of [5,15-bis{(10'-((triisopropylsilyl)ethynyl)-
9'-triptycenyl)ethynyl}-10,20-bis(3'-methoxycar-
bonylphenyl)porphyrinato]zinc(II) (18)
Synthesis of 5,15-bis(3'-methoxycarbonylphenyl)-
10,20-dibromoporphyrin (17b)
Dibromoporphyrin 17c (16 mg, 20 μmol) and triptycene 12
Porphyrin 17a [42] (100 mg, 0.173 mmol) was dissolved in (23 mg, 50 μmol) were placed in an oven-dried Schlenk flask
CHCl3 (150 mL) and degassed for 30 minutes. At 0 °C, and heated under vacuum. The flask was purged with argon and
N-bromosuccinimide (34 mg, 0.19 mmol) and pyridine anhydrous THF/NEt3 (1 mL :0.33 mL) were added by syringe.
(0.1 mL) were added. The reaction was stirred at room tempera- Argon was bubbled through the solution for five minutes.
774