First synthesis of sterically hindered cofacial bis(corroles) and their bis(cobalt) complexes

Abstract

Syntheses of face-to-face bis(corroles) exhibiting electronic interactions between the two chromophores.

References

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11. (a) ¹H NMR (CDCl₃) for 3: δ 8.84 (s, 4 H, meso H), [10.27 (s, 1 H), 8.40 (s, 1 H), 7.65 (d, 2 H), 7.54 (d, 2 H), 6.94 (dd, 2 H) anthracene H], 3.91 (m, 24 H, CH₂CH₃), 2.15 (s, 12 H, Me), 1.44 (m, 36 H, CH₂CH₃), –2.61 (s br, 6 H, NH); (b) C. Tardieux, C. P. Gros and R. Guilard, J. Heterocycl. Chem., 1998, in press.
12. Elemental analysis: Calc. for 6, C₄₉H₄₂N₄: C, 85.68; H, 6.16; N, 8.16. Found: C, 85.77; H, 6.21; N 7.80%. ¹H NMR (CDCl₃): δ 9.76 (s, 2 H, meso H⁵, H¹⁵), 9.50 (s, 1 H, meso H¹⁰), 7.88–6.96 (m, 20 H, Ph), 3.95 (q, 4 H, CH₂CH₃), 3.33 (s, 6 H, Me), 1.68 (t, 6 H, CH₂CH₃), –0.73 (s, NH), –1.47 (s, NH). IR : ν 3350 (NH), 2960 (CH), 2928 (CH), 2868 (CH) cm^–1. UV–VIS (CH₂Cl₂): λ_max(ε/dm³ mol^–1 cm^–1) 400 (83 400), 413 (74 700), 564 (19 400), 599 nm (20 900); UV–VIS (after HCl bubbling): λ_max(ε/dm³ mol^–1 cm^–1) 414 (95 900), 475 (15 000), 593 (39 500). MS (EI): m/z(%) 686 (100)[M]⁺, 343 [M]²⁺.
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14. Elemental analysis: Calc. for 8, C₁₁₂H₉₀N₈·3H₂O: C, 83.96; H, 6.04; N, 7.00. Found: C, 83.96; H, 6.00; N 6.78%. ¹H NMR (C₆D₆): δ 8.86 (s, 4 H, meso H), [8.79 (s, 1 H), 8.36 (d, ³J_H–H= 6.5, 2 H), 7.98 (s, 1 H) anthracene H], 7.80 (m, 8 H, Ph), [7.65 (d, ³J_H–H= 6.5, 2 H), 7.57 (dd, ³J_H–H= 6.5, 2 H) anthracene H], 7.52 (m, 8 H, Ph), 7.29 (m, 24 H, Ph), 3.27 (qd, ²J_H–H= 14.7, ³J_H–H= 7.5, 4 H, CH_AH_BCH₃), 3.22 (qd, ²J_H–H= 14.7 Hz, ³J_H–H= 7.5 Hz, 4 H, CH_AH_BCH₃), 1.95 (s, 12 H, Me), 1.31 (t, ³J_H–H= 7.5 Hz, 12 H, CH₂CH₃), –2.83 (s, 3 H, NH), –3.00 (s, 3 H, NH). IR : ν 3482 (NH), 3401 (NH), 2961 (CH), 2923 (CH), 2870 (CH) cm^–1. UV–VIS (CH₂Cl₂): λ_max(ε/dm³ mol^–1 cm^–1) 406 (171 000), 578 (44 500), 607 nm (37 000). MS (LSIMS): m/z 1549 [M + H]⁺.
15. Elemental analysis: Calc. for 9, C₁₁₀H₈₈N₈·2H₂O: C, 84.79; H, 5.96; N, 7.20. Found: C, 84.44; H, 5.98; N, 7.45%. ¹H NMR (C₆D₆): δ 9.59 (s, 4 H, meso H), [7.98 (d, 2 H), 7.61 (dd, 2 H), 7.47 (d, 2 H)] biphenylene H], 7.10 (m, 40 H, Ph), 3.54 (m, 8 H, Et), 3.07 (s, 12 H, Me), 1.52 (t, 12 H, Et), –2.80 (s, 3 H, NH), –3.00 (s, 3 H, NH). UV–VIS (CH₂Cl₂): λ_max(ε/dm³ mol^–1 cm^–1) 412 (142 000), 572 (34 000), 608 nm (33 000). MS (LSIMS): m/z 1523 [M + H]⁺.
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