3
1
1
Hz, 1H; -CHQC), 7.01 (d, Jtrans( H– H) ¼ 16.2 Hz, 1H; CQ
CH-), 6.00–6.15 (m, 2H; allyl-CHQ), 5.44 (dd, J ¼ 17.01, 1.62
Hz, 2H; allyl-Htrans), 5.27 (m, J ¼ 10.53, 1.35 Hz, 2H; allyl-
compound 2-ZnD, reactions of free base porphyrin 4-H2 (23
mg, 0.26 mmol) with Zn(OAc)2 ꢂ 2H2O (58 mg, 0.26 mmol) in a
mixture of CHCl3 : MeOH (10 : 2) resulted the title product
(22 mg, 92%) as a light green-purple solid. 1H NMR (270
MHz, CDCl3): d 9.64 (d, J ¼ 4.6 Hz, 2H; pyrrole-Hb), 9.11 (d,
J ¼ 4.6 Hz, 2H; pyrrole-Hb), 8.84 (d, J ¼ 4.86 Hz, 2H; pyrrole-
Hb), 8.63 (d, J ¼ 7.56 Hz, 1H; Ar-H), 8.12 (d, J ¼ 7.83 Hz, 1H;
Ar-H), 7.99 (d, J ¼ 8.1 Hz, 1H; Ar-H), 7.83 (d, J ¼ 8.1 Hz, 1H;
H
cis), 5.10 (t, J ¼ 7.02 Hz, 4H; -CH2), 4.62 (t, J ¼ 1.89 Hz, 2H;
Fc-H), 4.38 (t, J ¼ 1.62 Hz, 2H; Fc-H), 4.27 (s, 5H; Fc-H),
4.07 (dd, J ¼ 5.67, 1.35 Hz, 4H; CH2), 3.66 (t, J ¼ 5.67 Hz, 4H;
-CH2), 3.39 (s, 3H; N-Me), 2.83-2.74 (m, 4H; CH2), ꢁ2.65
ppm (s, 2H; inner-NH); 13C NMR (67 MHz, CDCl3): d 148.8
(Im-C2), 140.8 (Ph), 137.2 (Ph), 135.0 (CH-allyl), 134.8 (Ph),
132.0, 130.4, 129.0, 127.6 (br, pyrrole-b), 128.2 (Im-C4), 127.8
(Ph), 125.6 (Ph), 123.9 (Ph), 121.2 (Im-C5), 120.6, 119.2
(meso), 116.7 (CH2-allyl), 104.1 (meso), 83.3 (C-Cp), 77.5
(C-Cp), 72.0 (-OCH2), 69.3 (CH-Cp), 69.2 (-CH2-CHQ
CH2), 68.1 (CH-Cp), 67.1, 37.8 (CH2), 34.5 (CH3, N-CH3),
31.4 ppm (CH2); MALDI-TOF MS: found m/z ¼ 873.35 (M þ
H1), calculated for C54H52FeN6O2 872.35; IR (KBr): n 2922,
2852, 1104, 797 cmꢁ1; UV-Vis lmax (CH2Cl2) 420, 517, 552,
649 nm; fluorescence, lEM (CH2Cl2) 656, 720 nm (lEx 420 nm).
1
1
Ar-H), 7.26 (d, 3Jtrans( H– H) ¼ 16.2 Hz, 1H; -CHQC), 7.11 (d,
3Jtrans( H- H) ¼ 16.0 Hz, 1H; C¼CH-), 6.12–6.26 (m, 2H; allyl-
CHQ), 5.52 (dd, J ¼ 16.47, 1.62 Hz, 2H; allyl-Htrans), 5.49 (d,
J ¼ 1.62 Hz, 1H; Im-H5), 5.41 (d, J ¼ 4.59 Hz, 2H; pyrrole-
Hb), 5.32 (dd, J ¼ 10.53, 1.35 Hz, 2H; allyl-Hcis), 5.24 (t, J ¼
7.03 Hz, 4H; -CH2), 4.68 (t, J ¼ 1.62 Hz, 2H; Fc-H), 4.41 (t,
J ¼ 1.89 Hz, 2H; Fc-H), 4.32 (s, 5H; Fc-H), 4.22–4.24 (m, 4H;
-OCH2), 3.93–3.94 (m, 4H; -CH2), 2.99–3.11 (m, 4H; CH2),
1
1
2.14 (d, 1H, J ¼ 1.35 Hz; Im-H4), 1.67 ppm (s, 3H; N-Me); 13
C
NMR (67 MHz, CDCl3): d 151.0, 149.7, 148.9, 148.0 (pyrrole-
a), 146.1 (Im-C2), 142.7 (Ph), 136.7 (Ph), 135.2 (CH-allyl),
132.0, 128.2, 127.2, 127.0 (pyrrole-b), 129.2, 126.1, 121.2 (Im-
C4), 119.1 (meso), 117.7 (Im-C5), 116.7 (CH2-allyl), 96.1
(meso), 83.7, 72.1 (-OCH2), 70.1, 69.4 (-CH2-CHQCH2),
69.2, 67.1, 38.6 (CH2), 32.7 (N-CH3), 32.2, 31.7 (CH2),
22.74, 14.2 ppm; MALDI-TOF MS: found m/z ¼ 934.38 (M
þ H1), calculated for C54H50FeN6O2Zn 934.26; IR (KBr):
n 2920, 2852, 1483, 1340, 1104, 1002, 986, 789 cmꢁ1; UV-
Synthesis of 5,15-bis(3-allyloxypropyl)-10-{4-[2-(2,20,3,30,4,
40,5,50-octamethylferrocenenyl)ethenyl]phenyl}-20-(1-methylimi-
dazol-2-yl)porphyrin, 5-H2. Following the same reaction pro-
cedure as for compound 4-H2, samples of 17 (215 mg,
0.5 mmol), meso-(3-allyloxypropyl)dipyrromethane 8 (245
mg, 1.0 mmol) and 1-methyl-2-imidazolecarboxaldehyde 9
(55 mg, 0.5 mmol) in chloroform (180 mL) were reacted in
the presence of TFA (0.16 mL, 2.0 mmol) followed by
chloranil (370 mg, 1.5 mmol) oxidation to furnish a mixture
of porphyrin products. Purification by column chromatogra-
phy afforded the title compound 4-H2 in 17% yield. TLC
[Silica gel, acetone : CHCl3 (1 : 10)]: Rf ¼ 0.32; 1H NMR (270
MHz, CDCl3): d 9.53 (d, J ¼ 4.86 Hz, 2H; pyrrole-Hb), 9.48
(d, J ¼ 4.86 Hz, 2H; pyrrole-Hb), 8.98 (d, J ¼ 4.60 Hz, 2H;
pyrrole-Hb), 8.78 (d, J ¼ 4.86 Hz, 2H; pyrrole-Hb), 8.18 (d, J ¼
8.1 Hz, 1H; Ar-H), 8.10 (d, J ¼ 8.1 Hz, 1H; Ar-H), 7.84 (m,
2H; Ar-H), 7.68 (d, J ¼ 1.08 Hz, 1H; Im-H4), 7.47 (d, J ¼ 1.08
Vis
(CH2Cl2) 415, 440, 565, 622 nm.
max
Synthesis of 5,15-bis(3-allyloxypropyl)-10-{4-[2-(2,20,3,30,4,
40,5,50-octamethylferrocenenyl)ethenyl]phenyl}-20-(1-methylimi-
dazol-2-yl)porphyrinatozinc(II), 5-ZnD. Following a similar
procedure to that described for the synthesis of compound
4-ZnD, free base porphyrin 5-H2 reacted with
Zn(OAc)2 ꢂ 2H2O in a mixture of CHCl3 : MeOH (30 : 5)
for 3 h to afford the title compound 5-ZnD (24 mg, 90%) as a
purple solid after purification. 1H NMR (270 MHz, CDCl3): d
9.64 (d, J ¼ 4.6 Hz, 2H; pyrrole-Hb), 9.14 (d, J ¼ 4.60 Hz, 2H;
pyrrole-Hb), 8.95 (d, J ¼ 4.86 Hz, 2H; pyrrole-Hb), 8.62 (d, J ¼
8.1 Hz, 1H; Ar-H), 8.11 (d, J ¼ 8.1 Hz, 1H; Ar-H), 7.99 (d, J ¼
7.29 Hz, 1H; Ar-H), 7.85 (d, J ¼ 7.56 Hz, 1H; Ar-H), 7.24 (d,
3
1
1
Hz, 1H; Im-H5), 7.19 (d, Jtrans( H– H) ¼ 16.0 Hz, 1H;
3
1
1
-CH¼C), 7.00 (d, Jtrans( H– H) ¼ 16.2 Hz, 1H; -CH¼C), 6.15
–6.01 (m, 2H; allyl-CHQ), 5.45 (dd, J ¼ 17.28, 1.62 Hz, 2H;
allyl-Htrans), 5.28 (dd, J ¼ 10.26, 1.35 Hz, 2H; allyl-Hcis), 5.11
(t, J ¼ 7.02 Hz, 4H; -CH2), 4.08 (dd, J ¼ 5.4, 1.35 Hz, 4H;
-OCH2), 3.66 (t, J ¼ 6.0 Hz, 4H; -CH2), 3.43 (brs, 1H; CH-Cp),
3.40 (s, 3H; N-Me), 2.75–2.84 (m, 4H; CH2), 2.14, 1.90, 1.85,
1.80 (s, CH3, 24H; (CH3)8Fc), ꢁ2.63 ppm (brs, 2H; inner-
NH); 13C NMR (67 MHz, CDCl3): d 148.7 (Im-C2), 140.2
(Ph), 138.2 (Ph), 134.8 (CH-allyl), 134.7 (Ph), 132.0, 130.2,
129.0, 127.4 (br; pyrrole-b), 128.1 (Im-C4), 126.1 (Ph), 123.4
(Ph), 121.2 (Im-C5), 120.8, 120.4, 119.2 (meso), 116.7 (CH2-
allyl), 104.0 (meso), 82.0 (C-Cp), 81.0 (C-Cp), 79.5 (C-Cp),
77.1 (C-Cp), 71.9 (-OCH2), 71.4 (CH-Cp), 69.0 (-CH2-CHQ
CH2), 37.7 (CH2), 34.4 (N-CH3), 31.3 (CH2), 11.3, 11.2, 9.9,
9.5 ppm; MALDI-TOF MS: found m/z ¼ 985.48 (M þ H1),
calculated for C62H68FeN6O2 984.49; IR (KBr): n 2940, 2898,
2854, 1104, 1002, 964, 796, 740 cmꢁ1; UV-Vis lmax (CH2Cl2)
418, 514, 548, 646 nm; fluorescence, lEM (CH2Cl2) 655, 720 nm
(lEx 418 nm).
1
1
3Jtrans( H– H) ¼ 16.0 Hz, 1H; -CHQC), 7.09 (d, 3Jtrans(1H–1H)
¼
16.2 Hz, 1H; C¼CH-), 6.26–6.12 (m, 2H; allyl-CHQ), 5.55
(dd, J ¼ 10.26, 1.62 Hz, 2H; allyl-Htrans), 5.49 (d, J ¼ 1.62 Hz,
1H; Im-H5), 5.41 (d, J ¼ 4.86 Hz, 2H; pyrrole-Hb), 5.35 (dd,
J ¼ 10.26, 1.35 Hz, 2H; allyl-Hcis), 5.24 (m, 4H; -CH2), 4.22–
4.24 (m, 4H; -OCH2), 3.91–3.94 (m, 4H; -CH2), 3.52 (brs, 1H;
CH-Cp), 3.00–3.12 (m, 4H; CH2), 2.17, 1.92, 1.87, 1.82 (s,
24H; (CH3)8-Fc), 2.14 (d, 1H, J ¼ 1.35 Hz, Im-H4), 1.67 ppm
(s, 3H; N-Me); 13C NMR (67 MHz, CDCl3): d 150.9 149.7,
148.9, 147.8 (pyrrole-a), 146.0 (Im-C2), 142.1 (Ph), 137.7 (Ph),
135.2 (CH-allyl), 132.0, 129.1, 128.1 126.9 (pyrrole-b), 123.0,
122.9, 121.3, 121.2 (Im-C4), 119.0 (meso), 117.6 (Im-C5), 116.7
(CH2-allyl), 96.0 (meso), 83.7, 72.1 (-OCH2), 70.1, 69.4 (-CH2-
CH ¼ CH2), 69.2, 67.1, 38.6 (CH2), 32.7 (N-CH3), 32.2, 31.7
(CH2), 22.6, 15.2, 14.1, 10.7, 10.5, 9.3, 8.7 ppm; MALDI-TOF
MS: found m/z ¼ 1045.48 (M þ H1), calculated for C62H66Fe-
N6O2Zn 1045.39; IR (KBr: n 2941, 2900, 2853, 1628, 1428,
1340, 1104, 1002, 986, 788, 713 cmꢁ1; UV-Vis lmax (CH2Cl2)
413, 439, 564, 622 nm.
Synthesis of 5,15-bis(3-allyloxypropyl)-10-[4-(2-ferrocenyl)
ethenyl]phenyl}-20-(1-methylimidazol-2-yl)-porphyrinatozinc
(II), 4-ZnD. Following a similar procedure as described for
ꢀc
This journal is the Royal Society of Chemistry the Centre National de la Recherche Scientifique 2006
90 | New J. Chem., 2006, 30, 77–92