M. Davis et al. · Anthracenylporphyrins
1479
7.45 (m, 4H, phenyl-Hp and 6,3-anthracenyl-H), 7.73 (m, (5-Anthracenyl-10,15,20-trihexylporphyrinato)nickel(II)
2H, phenyl-Ho), 7.86, (d, 2H, J = 1.86 Hz, phenyl-Ho), 8.18 (16)
(d, 2H, J = 4.92 Hz, β-H), 8.26 (d, 2H, J = 8.69 Hz, 5,4-
Prepared via Suzuki cross-coupling approach to yield
anthracenyl-H), 8.62 (d, 2H, J = 4.89 Hz, β-H), 8.86 (m,
5
mg (0.006 mmol, 6 %) of orange crystals. M. p.
3H, β-H, 10-anthracenyl-H), 9.58 (d, J = 5.55 Hz, 2H, β-
H). – 13C NMR (100 MHz, CDCl3): δ = 31.48, 34.82, 114.6,
120.74, 121.14, 124.93, 125.66, 127.85, 128.04, 128.14,
128.63, 130.73, 132.35, 132.89, 133.31, 133.45, 134.3,
139.33, 142.12, 142.79, 143.53, 144, 148.88. – HRMS ((+)-
ESI): m/z = 996.3287 (calcd. 996.3277 or C46H29BrN4Ni,
[M+H]+).
≥ 300 ◦C. – Rf = 0.75. – UV/Vis (CH2Cl2): λmax(lgεmax) =
421 (1.66), 522 (0.67), 554 (0.59), 651 nm (0.363). –
1H NMR (400 MHz, CDCl3): δ = 0.759 (m, 9H,
C5H10,CH3), 1.47 (m, 6H, C4H8CH2CH3), 1.58 (m, 6H,
C3H6CH2CH2CH3), 1.87 (m, 6H, C2H6CH2C2H4CH3),
2.27 (m, 6H, CH2CH2C3H6CH3), 4.45 (t, J = 8.49 Hz, 4H,
CH2C4H8CH3), 4.57 (t, J = 8.49 Hz, 2H, CH2C4H8CH3),
6.99 (t, J = 8.23 Hz, 2H, 2,7-anthracenyl-H), 7.40 (d, J =
7.68 Hz, 2H, 1,8-anthracenyl-H), 7.65 (t, J = 8.20 Hz, 2H,
6,3-anthracenyl-H), 8.08 (d, J = 5.40 Hz, 2H, β-H), 8.2
(d, J = 9.61 Hz, 2H, 4,5-anthracenyl-H), 8.80 (s, 1H, 10-
anthracenyl-H), 9.01 (d, J = 5.40 Hz, 2H, β-H), 9.30 (d,
J = 5.40 Hz, 2H, β-H), 9.38 (d, J = 5.40 Hz, 2H, β-
H). – 13C NMR (100 MHz, CDCl3): δ = 13.55, 22.18,
23.23, 28.43, 28.76, 28.88, 29.19, 30.45, 31.27, 32.55, 38.22,
43.03, 52.98, 53.33, 62.72, 67.72, 128.24, 130.40, 131.88,
163.59, 167.30. – HRMS ((+)-ESI): m/z = 794.3893 (calcd.
794.3858 for C52H56N4Ni, [M+H]+).
5-Anthracenyl-10,15,20-trihexylporphyrin (14)
Prepared via Suzuki cross-coupling approach to yield
29 mg (0.04 mmol, 40 %) of purple crystals. M. p.
≥ 300 ◦C. – Rf = 0.69. – UV/Vis (CH2Cl2): λmax(lgεmax) =
421 (2.19), 519 (1.00), 551 (0.79), 600 (0.55), 660 nm
(0.53). – 1H NMR (400 MHz, CDCl3): δ = −2.31 (s, 2H,
NH), 0.95 (t, J = 7.40 Hz, 9H, C5H10CH3), 1.50 (m, 12H,
C3H6CH2CH2CH3), 2.57 (m, 6H, CH2CH2C3H8CH3), 4.94
(t, J = 7.99 Hz, 4H, CH2CH2C3H6CH3), 5.08 (t, J = 8.19 Hz,
2H, CH2C4H8CH3), 7.04 (t, J = 6.55 Hz, 2H, 2,7-anthracen-
yl-H), 7.14 (d, J = 9.01 Hz, 2H, 1,8-anthracenyl-H), 7.50 (t,
J = 7.37 Hz, 2H, 6,3-anthracenyl-H), 8.25 (d, J = 4.71 Hz,
2H, 4,5-anthracenyl-H), 8.35 (d, J = 9.01 Hz, 2H, β-H), 8.90
(s, 1H, 10-anthracenyl-H), 9.25 (d, J = 5.12 Hz, 2H, β-H),
9.55 (d, J = 4.91 Hz, 2H, β-H), 9.61 (d, J = 4.71 Hz, 2H, β-
H). – 13C NMR (100 MHz, CDCl3): δ = 13.76, 22.34, 29.89,
31.50, 34.97, 35.50, 38.25, 38.44, 112.43, 118.80, 119.67,
124.59, 125.21, 127.33, 127.80, 128.34, 130.51, 134.84,
136.00, 162.05. – HRMS ((+)-ESI): m/z = 738.4639 (calcd.
738.4661 for C52H58N4, [M+H]+).
5-Anthracenyl-15-bromo-10,20-dihexylporphyrin (17)
Prepared via Suzuki cross-coupling approach to yield
29.3 mg (0.04 mmol, 40 %) of purple crystals. M. p.:
≥ 300 ◦C. – Rf = 0.57. – UV/Vis (CH2Cl2): λmax(lgεmax) =
420 (2.92), 517 (1.79), 551 (1.46), 592 (1.30), 651 nm
1
(1.046). – H NMR (400 MHz, CDCl3): δ = −2.33 (s, 2H,
NH), 0.93 (t, J = 7.23 Hz, 6H, C5H10CH3), 1.40 (m, 4H,
C4H8CH2CH3), 1.51 (m, 4H, C3H6CH2CH2CH3), 1.81 (m,
4H, C2H4CH2C2H4CH3), 2.51 (m, 4H, CH2CH2C3H6CH3),
4.90 (t, J = 8.13 Hz, 4H, CH2C4H8CH3), 7.03 (t, J = 6.02 Hz,
2H, 2,7-anthracenyl-H), 7.09 (d, J = 8.74 Hz, 2H, 1,8-anthr-
acenyl-H), 7.49 (t, J = 7.53 Hz, 2H, 6,3-anthracenyl-H),
8.26 (d, J = 4.52 Hz, 2H, 4,5-anthracenyl-H), 8.33 (d, J =
8.74 Hz, 2H, β-H), 8.97 (s, 1H, 10-anthracenyl-H), 9.21 (d,
J = 4.22 Hz, 2H, β-H), 9.51 (d, J = 5.52 Hz, 2H, β-H), 9.80
(d, J = 5.12 Hz, 2H, β-H). – 13C NMR (100 MHz, CDCl3):
δ = 13.96, 22.54, 30.08, 31.71, 35.13, 38.56, 102.68, 114.75,
120.52, 124.90, 125.65, 127.87, 128.10, 128.48, 130.74,
135.04, 141.8, 142.0, 142.8. – HRMS ((+)-ESI): m/z =
732.9862 (calcd. 732.2828 for C46H45BrN4, [M+H]+).
(5-Anthracenyl-10,15,20-trihexylporphyrinato)zinc(II) (15)
Prepared via Suzuki cross-coupling approach to yield
46 mg (0.057 mmol, 57 %) of purple crystals. M. p.
◦
≥ 300 C. – Rf = 0.6. – UV/Vis (CH2Cl2): λmax(lgεmax) =
450 (2.11), 519 (0.51), 671 nm (1.12). – 1H NMR (400 MHz,
CDCl3): δ = 0.715 (m, 9H, C5H10,CH3), 1.43 (m, 6H,
C4H8CH2CH3), 1.51 (m, 6H, C3H6CH2CH2CH3), 1.75 (m,
6H, C2H6CH2C2H4CH3), 2.34 (m, 6H, CH2CH2C3H6CH3),
5.15 (t, J = 8.99 Hz, 4H, CH2C4H8CH3), 5.37 (t, J = 8.27 Hz,
2H, CH2C4H8CH3), 7.21 (t, J = 6.64 Hz, 2H, 2,7-anthr-
acenyl-H), 7.40 (d, J = 7.16 Hz, 2H, 1,8-anthracenyl-H),
7.85 (t, J = 6.94 Hz, 2H, 6,3-anthracenyl-H), 8.36 (m, 4H,
4,5-anthracenyl-H and β-H), 8.71 (s, 1H, 10-anthracenyl-
H), 9.14 (d, J = 4.63 Hz, 2H, β-H), 9.33 (d, J = 5.14 Hz,
5,15-Dianthracenyl-10,20-diphenylporphyrin (18)
Prepared via Suzuki cross-coupling approach to yield
2H, β-H), 9.47 (d, J = 5.12 Hz, 2H, β-H). – 13C NMR 28 mg (0.035 mmol, 35 %) of purple crystals. M. p.
◦
(100 MHz, CDCl3): δ = 10.98, 23.00, 23.74, 28.94, 23.74, ≥ 300 C. – Rf = 0.6. – UV/Vis (CH2Cl2): λmax(lgεmax) =
28.937, 29.73, 30.96, 31.96, 38.73, 46.10, 68.169, 128.82, 423 (3.05), 521 (1.85), 555 (1.65), 598 (1.45), 654 nm
130.91, 132.45, 167.80. – HRMS ((+)-ESI): m/z = 800.3818 (1.40). – 1H NMR (400 MHz, CDCl3): δ = −2.18 (s, 2H,
(calcd. 800.3796 for C52H56N4Zn, [M+H]+).
NH), 7.06 (t, J = 7.34 Hz, 4H, 7,2-anthracenyl-H), 7.16 (d,
Unauthenticated
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