Helvetica Chimica Acta – Vol. 91 (2008)
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HꢀC(7), HꢀC(18)); 8.49 (s, HꢀC(12), HꢀC(13)); 8.63 (d, J ¼ 4.6, HꢀC(8), HꢀC(17)). HR-ESI-MS:
882.2390 (Mþ, C52H42N4O6Znþ; calc. 882.2396).
[(2r,21c,3c)-21-(Ethoxycarbonyl)-5,10,15,20-tetrakis(3-methoxyphenyl)-2,3-dihydrocyclopropa[b]-
porphyrinato]zinc(II)1) (¼ [Ethyl (1a,1ab,19ab)-1a,19a-Dihydro-3,8,13,18-tetrakis(3-methoxyphenyl)-
1H,20H,22H-cyclopropa[b]porphine-1-carboxylato(2ꢀ)-kN20,kN21,kN22,kN23]zinc; 3b). UV/VIS
(CHCl3): 423 (5.51), 521 (3.87), 567 (3.83), 593 (4.01), 617 (4.47). 1H-NMR (500.13 MHz, CDCl3):
0.84 – 0.94 (m, MeCH2); 2.64 (t, J ¼ 8.2, HꢀC(21)); 3.90 (s, 4 MeO), 4.19 (q, J ¼ 6.1, MeCH2); 4.52 (d, J ¼
8.2, HꢀC(2), HꢀC(3)); 7.46 – 7.61 (m, 8 H, Hm (Ar), Hp (Ar)); 7.65 – 7.73 (m, 8 Ho (Ar)); 8.32 (d, J ¼ 4.6,
HꢀC(7), HꢀC(18)); 8.49 (s, HꢀC(12), HꢀC(13)); 8.60 (d, J ¼ 4.6, HꢀC(8), HꢀC(17)). HR-ESI-MS:
882.2390 (Mþ, C52H42N4O6Znþ; calc. 882.2396).
{2-[(Ethoxycarbonyl)methyl]-5,10,15,20-tetrakis(3-methoxyphenyl)porphyrinato]zinc(II) (¼ [Ethyl
5,10,15,20-Tetrakis(3-methoxyphenyl)-21H,23H-porphine-2-acetato(2ꢀ)-kN21,kN22,kN23,kN24]zinc; 4b).
UV/VIS (CHCl3): 420 (5.79), 484 (3.32), 510 (3.47), 547 (4.36), 583 (3.37). 1H-NMR (300.13 MHz,
CDCl3): 1.26 (t, J ¼ 7.1, MeCH2); 3.92 (s, 1 MeO), 3.95 – 3.96 (m, 3 MeO), 4.06 (s, HꢀC(21)); 4.15 (q, J ¼
7.1, MeCH2); 4.17 (q, J ¼ 7.13, MeCH2); 7.29 – 7.35 (m, 4 H, Hp (Ar)); 7.58 – 7.83 (m, 12 H, Ho (Ar), Hm
(Ar)); 8.77 (d, J ¼ 4.6, 1 HꢀC(b)); 8.86 (s, HꢀC(3)); 8.92 (d, J ¼ 4.6, 1 HꢀC(b)); 8.95 – 8.99 (m,
4 HꢀC(b)). HR-ESI-MS: 882.2390 (Mþ, C52H42N4O6Znþ; calc. 882.2396).
{5-[5-(Ethoxycarbonyl)-3-methoxycyclohepta-1,3,6-trien-1-yl]-10,15,20-tris(3-methoxyphenyl)por-
phyrinato}zinc(II) (¼{Ethyl 3-Methoxy-5-[10,15,20-tris(3-methoxyphenyl)-21H,23H-porphin-5-yl-
kN21,kN22,kN23,kN24]cyclohepta-2,4,6-triene-1-carboxylato(2ꢀ)}zinc; 5b). UV/VIS (CHCl3): 421 (5.69),
484 (3.29), 510 (4.48), 548 (4.32), 584 (3.45). 1H-NMR (500.13 MHz, CDCl3; see Fig. 2 for atom labels):
1.42 (t, J ¼ 7.1, MeCH2); 3.88 (s, 1 MeO); 4.13 (d, J ¼ 7.5, Hb); 4.46 (q, J ¼ 7.1, MeCH2); 6.04 (dd, J ¼ 9.7,
7.5, Hc); 6.56 (s, Ha); 6.78 (dd, J ¼ 9.7, 5.5, Hd); 7.19 (d, J ¼ 5.5, He); 7.63 (s, 3 Hp (Ar)); 7.76 – 7.81 (m, 9 H,
Ho (Ar), Hm (Ar)); 8.91 – 9.01 (m, 6 HꢀC(b)); 9.28 (d, J ¼ 4.6, 1 HꢀC(b)); 9.43 (d, J ¼ 4.6, 1 HꢀC(b)).
HR-ESI-MS: 882.2390 (Mþ, C52H42N4O6Znþ; calc. 882.2396).
[21,121-Bis(ethoxycarbonyl)-5,10,15,20-tetrakis(3-methoxyphenyl)-2,3,12,13-tetrahydrodicyclopro-
pa[b,l]porphyrinato]zinc(II) (¼{Diethyl 1a,9a,10a,18a-Tetrahydro-3,8,12,17-tetrakis(3-methoxyphenyl)-
1H,10H,19H,21H-dicyclopropa[b,l]porphine-1,10-dicarboxylato(2ꢀ)-kN19,kN20,kN21,kN22]zinc; 6b).
UV/VIS (CHCl3): 425 (100) 562 (7.4), 605 (10.9), 718 (12.9). HR-ESI-MS: 969.2836 ([M þ H]þ,
C56H49N4O8Znþ; calc. 969.2764).
[(2r,21t,3c)-21-(Ethoxycarbonyl)-5,10,15,20-tetrakis(pentafluorophenyl)-2,3-dihydrocyclopropa[b]-
porphyrinato]zinc(II)1) (¼ [Ethyl (1a,1aa,19aa)-1a,19a-Dihydro-3,8,13,18-tetrakis(2,3,4,5,6-pentafluoro-
phenyl)-1H,20H,22H-cyclopropa[b]porphine-1-carboxylato(2ꢀ)-kN20,kN21,kN22,kN23]zinc; 2c). UV/
VIS (CHCl3): 415 (5.57), 453 (3.06), 516 (3.90), 575 (3.89), 621 (4.88). 1H-NMR (500.13 MHz, CDCl3):
1.33 (t, J ¼ 7.1, MeCH2); 1.47 (t, J ¼ 2.7, HꢀC(21)); 4.31 (q, J ¼ 7.1, MeCH2); 4.37 (d, J ¼ 2.7, HꢀC(2),
HꢀC(3)); 8.32 (d, J ¼ 4.6, HꢀC(7), HꢀC(18)); 8.49 (s, HꢀC(12), HꢀC(13)); 8.61 (d, J ¼ 4.6, HꢀC(8),
HꢀC(17)). 19F-NMR (282.38 MHz, CDCl3): ꢀ 160.79 to ꢀ 160.88 (m, 4 Fo); ꢀ 160.99 to ꢀ 161.07 (m,
2 Fo); ꢀ 162.05 to ꢀ 162.17 (m, 2 Fo); ꢀ 175.58 (t, J ¼ 19.8, Fp); ꢀ 175.82 (t, J ¼ 19.8, 2 Fp); ꢀ 184.43 to
ꢀ 185.37 (m, 2 Fm); ꢀ 185.19 to ꢀ 185.37 (m, 6 Fm). HR-ESI-MS: 1123.0162 ([M þ H]þ,
C48H15F20N4O2Znþ; calc. 1123.0167).
[(2r,21c,3c)-21-(Ethoxycarbonyl)-5,10,15,20-tetrakis(pentafluorophenyl)-2,3-dihydrocyclopropa[b]-
porphyrinato]zinc(II)1) (¼ [Ethyl (1a,1ab,19ab)-1a,19a-Dihydro-3,8,13,18-tetrakis(2,3,4,5,6-pentafluoro-
phenyl)-1H,20H,22H-cyclopropa[b]porphine-1-carboxylato(2ꢀ)-kN20,kN21,kN22,kN23]zinc; 3c). UV/
1
VIS (CHCl3): 410 (100), 513 (2.5), 566 (8.3), 616 (17.0). H-NMR (500.13 MHz, CDCl3): 0.92 (t, J ¼
7.1, MeCH2); 2.52 (t, J ¼ 8.2, HꢀC(21)); 3.69 (q, J ¼ 7.1, MeCH2); 4.02 (d, J ¼ 8.2, HꢀC(2), HꢀC(3));
7.99 (d, J ¼ 4.6, HꢀC(7), HꢀC(18)); 8.28 (s, HꢀC(12), HꢀC(13)); 8.51 (d, J ¼ 4.6, HꢀC(8), HꢀC(17)).
19F-NMR (282.38 MHz, CDCl3): ꢀ 160.46 to ꢀ 161.12 (m, Fo); ꢀ 162.65 to ꢀ 162.98 (m, 2 Fo); ꢀ 175.73
to ꢀ 175.85 (m, 1 Fp); ꢀ 176.20 to ꢀ 176.45 (m, 2 Fp); ꢀ 176.63 to ꢀ 176.90 (m, 1 Fp); ꢀ 184.543 to
ꢀ 185.15 (m, 5 Fm); ꢀ 185.50 to ꢀ 185.98 (m, 3 Fm). HR-ESI-MS: 1123.0160 ([M þ H]þ,
C48H15F20N4O2Znþ; calc. 1123.0167).
{2-[(Ethoxycarbonyl)methyl]-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato}zinc(II) ( ¼ [Eth-
yl 5,10,15,20-Tetrakis(2,3,4,5,6-pentafluorophenyl)-21H,23H-porphine-2-acetato(2ꢀ)-kN21,kN22,kN23,
kN24]zinc; 4c). UV/VIS (CHCl3): 415 (5.73), 545 (4.39), 579 (3.87), 623 (3.14). 1H-NMR