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399
131.6 (2-quinoid), 129.3 (meso C), 119.9 (pyrrole
b-C), 82.7 (CH2CO2C(CH3)3), 47.2 (NCH2Ar), 35.5
(ring t-butyl quaternary C), 29.4 (ring t-butyl CH3), 28.0
(CH2CO2C(CH3)3); UV/Vis 325.2, 498.1; ESI-MS 1582
(MHþ).
quinoid H), 6.74 (dd, J¼7.6 Hz, 2.2, 4H, pyrroles bearing
NH), 6.65 (m, 2H, a pyrrole bearing NH), 6.54 (s, 2H,
pyrrole bearing NR), 4.08 (s, 2H, NCH2CO2), 1.35 (s, 18H,
ring t-butyl), 1.34 (s, 18H, ring t-butyl), 1.33 (s, 18H, ring
t-butyl), 1.27 (s, 18H, ring t-butyl), 1.22 (s, 9H, CH2CO2C-
(CH3)3); dC 186.2, 186.0 (quinoid CvO), 169.0 (COO),
147.3 (3-quinoid), 134.5, 133.9, 132.7, 131.8, 131.2, 130.5,
130.3, (120.8 (pyrrole b-C)), 81.8 (CH2CO2C(CH3)3), 35.6,
35.5, 35.3 (1:2:1, t-butyl quaternary C), 29.54, 29.48, 29.3
(t-butyl CH3), 28.1 (CH2CO2C(CH3)3); UV/Vis 329.9,
512.7; ESI-MS 1240 (MHþ).
1.2.3. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N21,N23-di((ethoxycarbonyl)-
methyl)porphyrinogen 5c. dH 9.26 (br s, 2H, NH), 7.58 (d,
J¼2.5 Hz, 4H, quinoid H), 7.35 (d, J¼2.5 Hz, 4H, quinoid
H), 6.83 (d, J¼2.3 Hz, 4H, pyrrole bearing NH), 6.56 (s, 4H,
pyrrole bearing NR), 3.99 (q, J¼7.1 Hz, 4H, ethyl CH2),
3.91 (s, 4H, NCH2CO2), 1.34 (s, 36H, t-butyl), 1.29 (s, 36H,
t-butyl), 1.05 (t, J¼7.1 Hz, 6H, ethyl CH3); dC 186.2
(quinoid CvO), 167.1 (COO), 148.5, 147.6 (3-quinoid),
137.6 (pyrrole (bearing NR) a-C), 134.9 (pyrrole (bearing
NH) a-C), 133.2 (1-quinoid), 132.0, 130.6 (2-quinoid),
129.8 (meso C), 119.5, 118.8 (pyrrole b-C), 62.1 (ethyl
CH2), 46.5 (NCH2CO2), 35.6, 35.4 (t-butyl quaternary C),
29.6, 29.5 (t-butyl CH3), 14.0 (ethyl CH3); UV/Vis 327.9,
502.8; ESI-MS 1298 (MHþ).
1.2.7. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N21,N22,N23-tri((ethoxycar-
bonyl)methyl)porphyrinogen 8c. Obtained in a mixture
with 3c. dH 7.61 (unresolved d, 2H, quinone H), 7.50
(d, J¼2.2 Hz, 2H, quinone H), 7.38 (s, 2H, quinone H),
7.34 (unresolved d, 2H, quinone H), 6.82 (d, J¼2.2 Hz,
2H, pyrrole H), 6.61 (s, 2H, pyrrole H), 6.50 (s, 2H,
pyrrole H, 6.44 (s, 2H, pyrrole H), 4.04–3.97 (m, 6H, CH2
of ethyl), 3.91 (broad s, 6H, NCH2), 1.35–126 (m, 72 H,
t-Bu), 1.10–1.03 (m, 9H, CH3 of ethyl); ESI-MS 1384
(MHþ).
1.2.4. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N21,N23-di(t-butoxycarbonyl)-
methyl)porphyrinogen 5d. dH 9.27 (br s, 2H, NH), 7.60 (d,
J¼ 2.3 Hz, 4H, quinoid H), 7.37 (d, J¼2.3 Hz, 4H, quinoid
H), 6.83 (d, J¼2.2 Hz, 4H, pyrrole bearing NH), 6.54 (s, 4H,
pyrrole bearing NR), 3.78 (s, 4H, NCH2CO2), 1.35 (s, 36H,
ring t-butyl), 1.29 (s, 36H, ring t-butyl), 1.22 (s, 18H,
CH2CO2C(CH3)3); dC 186.2 (quinoid CvO), 166.3 (COO),
148.5, 147.5 (3-quinoid), 137.7 (pyrrole (bearing NR) a-C),
135.0 (pyrrole (bearing NH) a-C), 133.2 (1-quinoid), 132.4,
130.6 (2-quinoid), 130.1 (meso C), 119.4, 118.4 (pyrrole
b-C), 83.1 (CH2CO2C(CH3)3), 47.5 (NCH2Ar), 35.6, 35.4
(t-butyl quaternary C), 29.6, 29.5 (ring t-butyl CH3), 27.9
(CH2CO2C(CH3)3); UV/Vis 328.0, 504.1; ESI-MS 1354
(MHþ).
1.2.8. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N21,N22,N23-tri(t-butoxycar-
bonyl)methyl)porphyrinogen 8d. Obtained in a mixture
with 3d. dH 7.61 (d, 2H, quinoid H), 7.51 (d, 2H, quinoid H),
7.36 (overlapping signals, 4H, quinoid H), 6.83 (d, 2H,
pyrrole H), 6.63 (s, 2H, pyrrole H), 6.48 (overlapping
signals, 4H, pyrrole H), 3.79 (m, 6H, NCH2), 1.57–1.22 (m,
99H, t-Bu); ESI-MS 1468 (MHþ).
1.2.9. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N21,N23,-di((ethoxycarbonyl)-
methyl)-N22,N24-dibenzylporphyrinogen 9. dH 7.46 (s,
4H, quinoid H), 7.25 (s, 4H, quinoid H), ,7.15 (m, 6H, m-
and p-Ar), 6.65–6.67 (m, 12H, pyrrole Hþo-Ar), 4.42
(s, 4H, NCH2Ar), 4.00 (q, J¼7.0 Hz, 4H, ethyl CH2), 3.92
(s, 4H, NCH2CO2), 1.30 (s, 36H, t-butyl), 1.25 (s, 36H,
t-butyl), 1.08 (t, J¼7.0 Hz, 6H, ethyl CH3); dC 186.1
(quinoid CvO), 167.2 (COO), 148.20, 148.17 (3-quinoid),
139.2, 138.0, 137.4, (134.5 (1-quinoid)), 131.6, 131.1
(2-quinoid), 129.7 (meso C), 128.7 (m-Ar), 128.0 (p-Ar),
125.9 (o-Ar), 120.6, 120.4 (pyrrole b-C)), 61.9 (ethyl CH2),
48.3 (NCH2Ar), 46.6 (NCH2CO2), 35.5, 35.4 (t-butyl
quaternary C), 29.4, 29.3 (t-butyl CH3), 14.2 (ethyl CH3);
UV/Vis 327.9, 500.0; ESI-MS 1478 (MHþ).
1.2.5. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N-((ethoxycarbonyl)methyl)-
porphyrinogen 7c. dH 10.24 (br s, 1H, NH), 9.05 (s, 2H,
NH), 7.65 (d, J¼2.1 Hz, 2H, quinoid H), 7.45 (d, J¼2.2 Hz,
2H, quinoid H), 7.42 (d, J¼2.0 Hz, 2H, quinoid H), 7.17 (d,
J¼1.9 Hz, 2H, quinoid H), 6.74 (dd, 4H, pyrroles bearing
NH), 6.69 (dd, 2H, a pyrrole bearing NH), 6.57 (s, 2H,
pyrrole bearing NR), 4.26 (s, 2H, NCH2CO2), 3.73 (q, J¼
7.1 Hz, 2H, ethyl CH2), 1.34 (s, 18H, t-butyl), 1.33 (s, 18H,
t-butyl), 1.32 (s, 18H, t-butyl), 1.27 (s, 18H, t-butyl), 1.01 (t,
J¼7.1 Hz, 3H, ethyl CH3); dC 186.1, 185.9 (ratio 3:1,
quinoid CvO), 166.2 (COO), 149.0, 148.2, 147.3 (ratio
1:1:2, 3-quinoid), 137.2 (pyrrole (bearing NR) a-C), 135.0,
134.4, 134.1, 132.8, 132.0, 131.84 (quinoid), 131.79
(quinoid), 131.3, 130.6, 130.4, 130.3, 120.6, 120.0, 117.7,
116.3 (pyrrole b-C)),(61.9 (ethyl CH2), 46.7 (NCH2CO2),
35.6, 35.5, 35.3 (1:2:1, t-butyl quaternary C), 29.50, 29.46
(t-butyl CH3), 13.8 (ethyl CH3); UV/Vis 330.1, 511.9;
ESI-MS 1212 (MHþ).
1.2.10. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N21,N23,-di((ethoxycarbonyl)-
methyl)-N22,N24-di(t-butoxycarbonyl)methyl)porphyri-
nogen 10. dH 7.49–7.50 (2 overlapping d, 8H, quinoid H),
6.64 (s, 4H, pyrrole bearing CH2CO2CH2CH3), 6.63 (s, 4H,
pyrrole bearing CH2CO2C(CH3)3), 4.00 (q, J¼7.1 Hz, 4H,
ethyl CH2), 3.83 (s, 4H, NCH2CO2Et), 3.69 (s, 4H,
NCH2COt2Bu), 1.32 (s, 36H, ring t-butyl), 1.31 (s, 36H,
ring t-butyl), 1.25 (s, 18H, CH2CO2C(CH3)3), 1.07 (t, J¼
7.1 Hz, 6H, ethyl CH3); dC 186.2 (quinoid CvO), 167.1,
166.3 (COO), 148.3, 148.2 (3-quinoid), 138.7 (pyrrole a-C),
135.1 (1-quinoid), 131.6, 131.3 (2-quinoid), 129.1, 128.7
(meso C), 120.05, 119.96 (pyrrole b-C), 82.8 (CH2CO2C-
(CH3)3), 61.8 (ethyl CH2), 47.2, 46.3 (NCH2), 35.5 (ring
1.2.6. meso-Tetrakis-5,10,15,20-(3,5-di-t-butyl-4-oxa-
cyclohexa-2,5-dienylene)-N-(t-butoxycarbonyl)methyl)-
porphyrinogen 7d. dH 10.44 (br s, 1H, NH), 8.91 (s, 2H,
NH), 7.67 (d, J¼2.3 Hz, 2H, quinoid H), 7.45 (hidden d, 2H,
quinoid H), 7.44 (hidden d, 2H, quinoid H), 7.35 (br s, 2H,