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HAr + HNH), 7.47 (s, 1H, HNH), 7.30 (s, 1H, HNH), 6.75 (d, J = 7.5 Hz,
122.85, 122.48, 115.88, 115.62, 98.52, 82.22, 82.18, 80.18, 78.13,
1H, HAr), 6.62–6.57 (m, 3H HAr), 6.50–6.39 (m, 4H, HAr), 6.38–6.29 (m,
78.07, 75.87, 73.75, 70.24, 68.78, 66.26, 55.60, 52.82. IR νmax (CH2Cl2)/
4H, HAr), 6.01–5.94 (m, 2H, HAr), 5.66–5.61 (m, 2H, HAr), 2.97 (s, 1H, cm–1: 1047, 1096, 1266, 1306, 1449, 1518, 1582, 1680, 2929, 2960,
HCH2-N3), 2.81 (m, 2H, HCH2-N3), 2.65 (d, J = 13.8, 1H, HCH2-N3), 2.55
(m, 3H, HCH2-N3), 2.12 (s, 1H, HCH2-N3). 13C NMR (300 MHz, CDCl3, 549 (3.70), 591 (3.76), 647 (3.51). HR-MS (MALDI): m/z
298 K): δ = 164.75, 152.00, 151.26, 150.78, 138.75, 132.88, 130.28,
(C200H190N20O28) calcd. 3321.41, found [M + Na]+ 3344.3. Elemental
3033, 3417. UV/Vis λmax (CH2Cl2)/nm (log ε): 424 (5.50), 521 (4.24),
123.39, 126.36, 123.58, 121.08, 115.88, 52.82, 52.69, 52.38. IR νmax analysis calcd. for C200H190N20O28: C, 72.32; H, 5.77; N, 8.43; found
(CH2Cl2)/cm–1: 996, 1250, 1308, 1447, 1518, 1581, 1681, 2101, 2340, C, 72.01; H, 5.88; N, 8.31.
2360, 3415. UV/Vis λmax (CH2Cl2)/nm (log ε): 425 (5.58), 556 (4.30),
General procedure for the synthesis of iron(III) complexes. FeBr2
(1.42 mmol) was added to a THF (20.0 mL) solution of porphyrin
592 (1.20), 626 (2.78) (1.20). LR-MS (ESI): m/z (C76H52N20O4Zn) calcd.
1372.38; found [M + Na]+ 1396.4. Elemental Analysis calcd. for
(7.12 × 10–2 mmol) under nitrogen. The solution was refluxed at
C76H54N20O4Zn: C, 66.30; H, 3.95, N, 20.35; found C, 66, 54; H, 3.99;
75 °C for 5 hours until the complete consumption of the starting
porphyrin observed by TLC (Al2O3, CH2Cl2/MeOH = 97:3). The sol-
vent was evaporated to dryness under vacuum and the residue
purified by chromatography (Al2O3, eluent CH2Cl2/MeOH, 97:3) to
N, 20.16.
Synthesis of Zn(7). Zn(5) (150.0 mg, 1.11 × 10–1 mmol) and 6
(276.0 mg, 5.54 × 10–1 mmol) were dissolved in THF (20.0 mL) and
then a solution of CuSO4·5H2O (137.0 mg, 5.54 × 10–1 mmol) in H2O
yield a brown solid corresponding to the iron complex. Finally, all
(5.0 mL) was added. A solution of sodium ascorbate (109.0 mg,
5.54 × 10–1 mmol) in H2O (5 mL) was added and the resulting mix-
ture was stirred for 5 hours at 50 °C until the complete consumption
of Zn(5) was observed by TLC (SiO2, CH2Cl2/MeOH = 97:3). The mix-
ture was extracted with CH2Cl2 (3 × 20.0 mL), dried with Na2SO4
and filtered. The solvent was evaporated to dryness under vacuum
and the residue purified by flash chromatography (SiO2, gradient
elution from CH2Cl2 to CH2Cl2/MeOH, 98:2) to yield the purple solid
7 (232.0 mg, 63 %). 1H NMR (400 MHz, CDCl3, 298 K): δ = 8.98–8.75
(m, 12 H, Hꢀpyrr + HAr), 8.09 (t, J = 6.6 Hz, 4H, HAr),7.85–7.81 (m, 8H,
the iron complexes were treated at 50 °C with MeOH for 8 h. The
solvent was evaporated to dryness to afford the desired compound.
Fe(F5TPP)(OMe) 92 % yield. IR νmax (CH2Cl2)/cm–1: 1091, 1277,
1273, 1420, 2854, 2927, 3054, 3059. UV/Vis λmax (MeOH)/nm (log ε):
413 (3.7), 478 (2.8), 484 (2.8). LR-MS (ESI): m/z (C45H26F5FeN4O) calcd.
789.14; found [M – OMe] 759.18. Elemental analysis calcd. for
C45H26FeN4O: calcd. C, 68.45; H, 3.32; N, 7.10; found C, 68.67;
H, 3.63; 6.96.
Fe(2)(OMe) 90 % yield. IR νmax (CH2Cl2)/cm–1: 1026, 1092, 1271,
1280, 1422, 2927, 2961, 3056. UV/Vis λmax (MeOH)/nm (log ε):
413 nm (5.7), 495 (3.6), 600 (3.4). LR-MS (ESI) m/z:
(C100H85F4FeN4O12) calcd. 1665.54, found [M + Na]+ 1688.59. Ele-
mental analysis calcd. for C100H85F4FeN4O12 C 72.07, H 5.14, N 3.36;
found C, 72.25; H, 5.35; N, 3.30.
Fe(3)(OMe) 95 % yield. IR νmax (CH2Cl2)/cm–1: 1081, 1259, 1266,
1278, 2857, 2926, 3058. UV/Vis λmax (MeOH)/nm (log ε): 410 (5.1),
519 (3.8), 580 (3.7). HR-MS (MALDI): m/z (C265H249F16FeN4O45) calcd.
4566.64, found [M – OMe+Na]+ 4559.2. Elemental analysis calcd. for
C265H249F16FeN4O45 C, 69.65; H, 5.49; N, 1.23; found C, 69.83; H, 5.62,
N, 1.21.
Fe(7)(OMe) 92 % yield. IR νmax (CH2Cl2)/cm–1: 1447, 1452, 1512,
1582, 1680, 2867, 2928, 2960, 3417. UV/Vis λmax (CH2Cl2)/nm (log ε)
421 (5.43), 478 (4.78), 581 (4.39). HR-MS (MALDI): m/z
(C201H191FeN20O28) calcd. 3406.35, found [M – OMe] 3375.0. Elemen-
tal analysis calcd. for C201H191FeN20O28: C 70.87, H 5.65, N 8.22;
found C 70.97, H 5.75, N 8.15.
HAr + HNH), 7.75 (s, 1H, HNH), 7.61 (s, 1H, HNH), 7.52–6.94 (m, 88H,
HAr + Hsolvent), 6.82–6.74 (m, 4H, HAr), 6.66–6.47 (m, 12H, HAr), 6.26–
6.18 (m, 3H, HAr), 5.84–5.72 (m, 4H, HCH2), 5.52–5.48 (m, 2H, HCH2),
5.41–5.34 (m, 2H, HCH2), 5.01–4.92 (m, 1H, Hsugar), 4.84 (d, J =
11.2 Hz, 2H, Hsugar), 4.72 (q, J = 9.5, 7.8 Hz, 6H, Hsugar), 4.66–4.52 (m,
9H, Hsugar), 4.49–4.24 (m, 12H, Hsugar), 4.22–4.14 (m, 2H, Hsugar),
4.05–3.97 (m, 2H, Hsugar), 3.78 (t, J = 9.2 Hz, 2H, Hsugar), 3.69–3.62
(m, 1H, Hsugar), 3.57–3.39 (m, 8H, Hsugar), 3.31–3.29 (m, 12H, Hsugar),
3.23–3.13 (m, 1H, Hsugar), 3.04 (d, J = 11.6 Hz, 1H, Hsugar), 2.93 (t, J =
9.4 Hz, 1H, Hsugar). 13C NMR (100 MHz, CDCl3, 298 K): δ = 139.42,
139.10, 138.41, 128.86, 128.68, 128.50, 128.34, 128.05, 127.89,
119.49, 99.34, 98.47, 82.28, 81.98, 81.42, 80.17, 73.75, 70.67, 70.15,
68.77, 65.58, 65.45, 63.73, 55.99, 52.76. IR νmax (CH2Cl2)/cm–1: 1047,
1091, 1223, 1273, 1362, 1446, 1519, 1582, 1712, 2928, 3060, 3411.
UV λmax (CH2Cl2)/nm (log ε): 434 (5.20), 563 (4.08), 602 (3.51). HR-MS
(MALDI): m/z (C200H188N20O28Zn) calcd. 3383.33, found [M] 3383.6.
Elemental Analysis calcd. for C200H188N20O28Zn: C, 70.96; H, 5.60;
N, 8.28; found C, 71.06; H, 5.70; N, 8.20.
Synthesis of Ru(F5TPP)(CO) and Ru(2)(CO). Ru3CO12
(2.13 × 10–1 mmol) was added to a 1,2,4-trichlorobenzene (20.0 mL)
solution of porphyrin (7.12 × 10–2 mmol) under nitrogen. The solu-
tion was refluxed for 5 hours until the complete consumption of
the starting porphyrin was observed by TLC (SiO2, n-hexane/
AcOEt = 7:3). The solvent was evaporated to dryness under vacuum
and the residue purified by chromatography (SiO2, gradient elution
from n-hexane to n-hexane/AcOEt = 7:3) to yield a red solid corre-
sponding to the ruthenium complex.
Synthesis of 7. HCl 37 % (30.0 mL) was added to a AcOEt
(120.0 mL) solution of Zn(7) (200.0 mg, 5.92 × 10–2 mmol). The re-
sulting solution was stirred for 3 hours at room temperature until
the complete consumption of Zn(7) was observed by TLC (SiO2,
CH2Cl2/MeOH = 97:3), then H2O (100.0 mL) was added to the mix-
ture. The organic phase was extracted with H2O (3 × 100.0 mL) until
pH = 7. The resulting solution was dried with Na2SO4 and filtered.
The solvent was evaporated to dryness under vacuum to yield the
purple solid 7 (195.0 mg, 99 %). 1H NMR (400 MHz, CDCl3, 298 K):
δ = 8.91–8.82 (m, 8H, Hꢀpyrr), 8.77–8.59 (m, 4H, HAr), 7.93–7.83 (m,
9H, HAr), 7.72 (s, 2H, Htriazo), 7.51–7.48 (m, 5H, HAr + Htriazo), 7.31–
7.07 (m, 63H, HAr + Hsolvent), 6.89–5.86 (m, 19H, HAr), 4.91–4.26 (m,
Ru(F5TPP)(CO) 68 % yield. 1H NMR (300 MHz, CDCl3): δ = 8.78 (d,
J = 4.9 Hz, 2H, Hꢀpyrr), 8.69 (s, 4H, Hꢀpyrr), 8.61 (d, J = 4.9 Hz, 2H,
H
ꢀpyrr), 8.25–8.09 (m, 6H, HAr), 7.82–7.67 (m, 9H, HAr). 19F NMR
46H, Hsugar), 3.85–3.79 (t, J = 9.2 Hz, 4H, Hsugar), 3.59 –3.49 (m, 20H, (282 MHz, CDCl3): δ = –136.62 (dd, J = 24.2, 9.0 Hz, 1F), –138.24 (d,
Hsugar), 3.33 (s, 12H, HOMe), –2.64 (s, 2H, NHpyrr). 13C NMR (100 MHz,
CDCl3, 298 K): δ = 165.14, 145.69, 145.57, 139.16, 138.73, 138.54,
138.67, 138.45, 138.38, 138.35, 135.89, 135.55, 135.49, 135.35,
135.20, 130.91, 130.67, 130.60, 128.86, 128.78, 128.75, 128.70,
128.64, 128.52, 128.33, 128.25, 128.20, 128.13, 128.07, 127.95,
127.90, 127.85, 127.79, 127.74, 127.33, 126.97, 126.04,125.56, 124.21,
J = 24.3 Hz, 1F), –153.73 (t, J = 21.0 Hz, 1F), –162.48 (t, J = 23.4 Hz,
1F), –163.06 (d, J = 23.9 Hz, 1F). 13C NMR (75 MHz, CDCl3): δ =
144.59, 144.18, 144.15, 143.16, 142.09, 142.03, 138.76, 134.41,
133.81, 133.37, 132.24, 131.90, 129.48, 128.04, 127.56, 126.97,
126.70, 126.64, 126.49, 123.97, 123.54, 122.53. IR νmax (CH2Cl2)/cm–1
:
1010, 1094, 1273, 1282, 1494, 1520, 1942, 2962, 3004, 3056, 3063,
Eur. J. Inorg. Chem. 0000, 0–0
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