Unsymmetrical meso-Substituted Porphyrin Dimers and Arrays
= 4.8 Hz, 2 H, Hβ), 8.97 (m, 8 H, Hβ) ppm. 13C NMR (150 MHz,
CDCl3): δ = 14.1, 22.7, 29.4, 31.9, 41.0, 126.6, 126.7, 127.7, 128.8,
134.4 ppm. UV/Vis (CH2Cl2): λmax (logε) = 406 (5.20), 503 (3.94),
533 (3.53), 574 nm (3.48). HRMS (MALDI-TOF) m/z calcd. for
C79H56N8O3 [M]+ 1165.4554; found 1165.4497.
(4.97), 452 (4.10), 525 (4.34), 564 (3.96), 601 (3.87), 661 nm (3.79).
HRMS (MALDI) m/z calcd. for C79H81N8O3 [M + H]+ 1189.6432;
found 1189.6471.
5-Butyl-10,20-bis(4-methoxyphenyl)-15-(10Ј,15Ј,20Ј-triphenylpor-
phyrin-5Ј-ylethynyl)porphyrin (98): Produced from 69 (10 mg,
0.018 mmol), 23 (12 mg, 0.018 mmol), AsPh3 (4 mg, 0.013 mmol),
5-Butyl-10,15-bis(4-methoxyphenyl)-20-(10Ј,15Ј,20Ј-triphenylpor-
phyrin-5Ј-yl)porphyrin (95):[48] Produced from 79 (10 mg, and Pd2(dba)3 (5 mg, 0.001 mmol) following procedure J. After pu-
0.015 mmol), 23 (10 mg, 0.015 mmol), Cs2CO3 (10 mg, 0.05 mmol), rification dark green crystals were isolated (5 mg, 0.004 mmol,
and Pd(PPh3)4 (2 mg, 0.002 mmol) following general procedure E 29%); m.p. Ͼ 300 °C. 1H NMR (400 MHz, CDCl3, TMS): δ =
1
3
to give a green solid (9 mg, 0.008 mmol, 48%); m.p. Ͼ 300 °C. H
–2.02 (s, 2 H, NH), –1.93 (s, 2 H, NH), 1.15 (t, JH,H = 7.4 Hz, 6
NMR (400 MHz, CDCl3, TMS): δ = –2.23 (s, 2 H, NH) –2.15 (s,
H, CH3), 1.88–1.81 (m, 2 H, CH2), 2.57–2.51 (m, 2 H, CH2), 4.14
(s, 6 H, OCH3), 4.98 (m, 2 H, CH2), 7.35 (m, 4 H, Ar-H), 7.80 (m,
2 H, NH), 1.18–1.22 (t, 3JH,H = 14.7 Hz, 3 H, CH3), 1.87 (m, 2 H,
CH2), 2.60 (m, 2 H, CH2), 4.05 (s, 6 H, OCH3), 5.13 (m, 2 H, CH2), 9 H, Ph-H), 8.17 (m, 4 H, Ar-H), 8.22 (m, 2 H, Ph-H), 8.29 (m, 4
3
3
7.23–7.35 (d, JH,H = 8.8 Hz, 4 H, Ar-H), 7.71 (m, 6 H, Ph-H), H, Ph-H), 8.80 (m, 4 H, Hβ), 8.90–8.91 (d, JH,H = 4.7 Hz, 2 H,
3
3
7.84 (m, 2 H, Ph-H), 8.04–8.05 (d, JH,H = 4.9 Hz, 2 H, Ph-H), Hβ), 9.07 (m, 4 H, Hβ), 9.44 (d, JH,H = 4.8 Hz, 2 H, Hβ), 10.24
8.12 (d, JH,H = 8.6 Hz, 6 H, Ar-H), 8.23 (m, 4 H, Hβ), 8.31–8.33
(d, JH,H = 5.4 Hz, 2 H, Ph-H), 8.60 (m, 4 H, Hβ), 8.91 (m, 4 H,
Hβ), 9.02–9.03 (d, JH,H = 4.9 Hz, 2 H, Hβ), 9.61–9.62 (d, JH–H
4.9 Hz, 2 H, Hβ) ppm. UV/Vis: λmax (logε) = 430 (4.90), 522 (3.58),
558 (3.60), 605 nm (3.65). HRMS (MALDI-TOF) m/z calcd. for
C76H59N8O2 [M + H]+ 1115.4761; found 1115.4783.
3
3
3
(d, JH,H = 4.7 Hz, 2 H, Hβ), 10.32 (d, JH,H = 4.7 Hz, 2 H, Hβ)
ppm. 13C NMR (150 MHz, CDCl3): δ = 14.0, 14.1, 22.5, 23.5, 29.2,
29.6, 29.9, 31.8, 55.5, 112.2, 120.7, 127.8, 128.2, 128.7, 128.8, 130.3,
134.3, 134.4, 134.7, 135.4, 141.7 ppm. UV/Vis (CH2Cl2): λmax (logε)
= 415 (4.73), 470 (4.72), 518 (3.89), 620 (3.93), 717 nm (4.00).
HRMS (MALDI-TOF) m/z calcd. for C7 8H58 N8 O2 [M]+
1138.4683; found 1138.4803.
3
3
3
=
10,15,20-Tris(4-methoxyphenyl)-5-(10Ј,15Ј,20Ј-trihexylporphyrin-5Ј-
yl)porphyrin (96): Produced from 80 (10 mg, 0.015 mmol), 22
(12 mg, 0.02 mmol), Cs2CO3 (4 mg, 0.02 mmol), and Pd(PPh3)4
(3 mg, 0.003 mmol) following general procedure E to give a green
solid (6 mg, 0.005 mmol, 37 %); m.p. Ͼ 300 °C. 1H NMR
10,15,20-Tris(3-methoxyphenyl)-5-(5Ј,10Ј,20Ј-triphenylporphyrin-
5Ј-ylethynyl)porphyrin (99): Produced from 69 (10 mg,
0.018 mmol), 21 (13 mg, 0.018 mmol), AsPh3 (5 mg, 0.020 mmol),
and Pd(PPh3)4 (2 mg, 0.001 mmol) following procedure J. After pu-
(400 MHz, CDCl3, TMS): δ = –2.14 (s, 2 H, NH), –2.05 (s, 2 H, rification dark green crystals were isolated (3 mg, 0.002 mmol,
NH), 0.91–0.82 (m, 12 H, CH2), 1.38 (m, 6 H CH2), 1.45 (m, 6 H, 29%); m.p. Ͼ 300 °C. 1H NMR (400 MHz, CDCl3, TMS): δ =
CH2), 1.76 (m, 4 H, CH2), 1.92 (m, 2 H, CH2), 2.54 (m, 4 H, CH2), –2.03 (s, 2 H, NH) –2.01 (s, 2 H, NH), 3.98 (s, 3 H, OCH3), 4.01
3
2.63 (m, 2 H, CH2), 4.04 (s, 6 H, OCH3), 4.18 (s, 3 H, OCH3), 4.94 (s, 6 H, OCH3), 7.10 (d, JH,H = 15.9 Hz, 4 H, Ar-H), 7.63 (m, 6
3
(m, 4 H, CH2), 5.11–5.15 (t, 3JH,H = 15.6 Hz, 2 H, CH2), 7.24–7.25 H, Ph-H), 7.75 (d, JH,H = 15.9 Hz, 4 H, Ar-H), 7.91–7.87 (m, 3
3
3
(d, JH,H = 8.3 Hz, 4 H, Ph-H), 7.38–7.39 (d, JH,H = 8.3 Hz, 2 H,
H, Ph-H), 8.24–8.20 (m, 3 H, Ph-H), 8.32–8.27 (m, 4 H, Ph-H),
8.83–8.81 (m, 3 H, Hβ), 8.87–8.85 (m, 3 H, Hβ), 8.95–8.90 (m, 3
H, Hβ), 9.11–9.08 (m, 2 H, Hβ), 9.15–9.12 (m, 2 H, Hβ), 9.35–9.32
(m, 1 H, Hβ), 10.37–10.32 (m, 4 H, Hβ) ppm. 13C NMR (150 MHz,
3
3
Ph-H), 8.05–8.06 (d, JH,H = 4.9 Hz, 2 H, Hβ), 8.08–8.09 (d, JH,H
= 4.4 Hz, 2 H, Hβ), 8.16–8.18 (d, 3JH,H = 8.8 Hz, 4 H, Ph-H) 8.25–
3
3
8.26 (d, JH,H = 8.3 Hz, 2 H, Ph-H) 8.63–8.64 (d, JH,H = 4.9 Hz,
3
2 H, Hβ), 8.96–8.97 (d, JH,H = 4.9 Hz, 2 H, Hβ), 9.00–9.01 (d, CDCl3): δ = 14.0, 22.5, 22.6, 29.2, 29.7, 29.9, 31.8, 55.5, 125.3,
3JH,H = 4.9 Hz, 2 H, Hβ), (m, 4 H, Hβ), 9.13–9.14 (d, JH,H
=
126.7, 127.5, 127.9, 128.2, 128.8, 130.3, 134.3, 134.4, 136.7,
3
4.4 Hz, 2 H, Hβ), 9.58–9.60 (d, 3JH,H = 4.0 Hz, 2 H, Hβ), 9.66–9.67 143.2 ppm. UV/Vis (CH2Cl2): λmax (logε) = 412 (4.91), 473 (4.88),
3
(d, JH,H = 4.9 Hz, 2 H, Hβ) ppm. 13C NMR (150 MHz, CDCl3):
δ = 13.9, 14.0, 22.5, 22.7, 29.5, 29.6, 30.1, 30.2, 31.7, 31.9, 38.5,
55.3, 112.0, 112.1, 135.3 ppm. UV/Vis (CH2Cl2): λmax (logε) = 410
(5.67), 450 (5.01), 507 (4.48), 567 (3.95), 599 (3.87), 666 nm (3.49).
HRMS (MALDI-TOF) m/z calcd. for C79H81N8O3 [M + H]+
1189.6432; found 1189.6428.
517 (4.01), 620 (4.09), 713 nm (4.19). HRMS (MALDI-TOF) m/z
calcd. for C81H56N8O3 [M]+ 1188.4475; found 1188.4490.
10,20-Bis(3,5-di-tert-butylphenyl)-15-phenyl-5-[5Ј,10Ј,20Ј-tris(4-
methoxyphenyl)porphyrin-5Ј-ylethynyl]porphyrin (100): Following
procedure J, 71 (20.0 mg, 0.025 mmol), 22 (18 mg, 0.025 mmol),
AsPh3 (10 mg, 0.033 mmol), and Pd2(dba)3 (2 mg, 0.003 mmol)
were dried in vacuo and dissolved in degassed NEt3 (1 mL) and
THF (4 mL). The solution was stirred for 14 h at 65 °C. All sol-
vents were removed and the residue purified by column chromatog-
10,15,20-Tris(3-methoxyphenyl)-5-(10Ј,15Ј,20Ј-trihexylporphyrin-5Ј-
yl)porphyrin (97): Produced from 80 (10 mg, 0.015 mmol), 21
(8 mg, 0.01 mmol), Cs2CO3 (4 mg, 0.02 mmol), and Pd(PPh3)4
(2 mg, 0.002 mmol) following general procedure E to give a purple
raphy (silica, CH2Cl2/hexane, 1:4 to 2:1, v/v) to yield a red-green
1
1
solid; yield = 8 mg (0.007 mmol, 51%); m.p. Ͼ 300 °C. H NMR solid; yyield 23 mg (0.016 mmol, 64%); m.p. Ͼ 300 °C. H NMR
(400 MHz, CDCl3, TMS): δ = –2.16 (s, 2 H, NH) –2.07 (s, 2 H, (400 MHz, CDCl3, TMS): δ = –1.92 (s, 2 H, NH), –1.89 (s, 2 H,
NH), 0.86 (m, 12 H, CH3), 1.00 (m, 6 H CH2), 1.36–1.30 (m, 8 H, NH), 1.59 (s, 36 H, tBu–H), 4.11 (s, 3 H, CH3), 4.14 (s, 6 H, CH3),
CH2), 1.77 (m, 4 H, CH2), 1.92–1.86 (m, 2 H, CH2) 2.50 (m, 4 H, 7.31 (d, JH,H = 8.2 Hz, 2 H, Ph-H), 7.31 (d, JH,H = 8.8 Hz, 4 H,
CH2), 2.62 (m, 2 H, CH2), 4.01 (s, 6 H, OCH3), 4.14 (s, 3 H, Ph-H), 7.74–7.80 (m, 3 H, Ph-H), 7.85–7.89 (m, 4 H, Ph-H), 8.15
3
3
OCH3), 4.94–4.85 (m, 4 H, CH2), 5.14–5.06 (m, 2 H, CH2), 7.21
(d, 3JH,H = 8.2 Hz, 2 H, Ph-H), 8.17–8.21 (m, 4 H, Ph-H), 8.23 (d,
3JH,H = 8.8 Hz, 4 H, Ph-H), 8.84–8.93 (m, 8 H, Hβ), 9.17 (d, 3JH,H
3
3
(d, JH,H = 8.6 Hz, 4 H, Ph-H), 8.03 (d, JH,H = 4.7 Hz, 2 H, Hβ),
3
3
3
8.07 (d, JH,H = 4.7 Hz, 2 H, Hβ), 8.14 (d, JH,H = 8.6 Hz, 4 H,
= 4.6 Hz, 2 H, Hβ) 9.20 (d, JH,H = 4.7 Hz, 2 H, Hβ) 10.40 (m, 4
Ph-H), 8.22 (d, JH,H = 8.3 Hz, 2 H, Hβ), 8.61 (d, JH,H = 4.7 Hz, H, Hβ) ppm. 13C NMR (150 MHz, CDCl3): δ = 35.2, 55.6, 55.6,
3
3
3
3
2 H, Hβ), 8.96 (dd, JH,H = 13.2, 4.7 Hz, 4 H, Hβ), 9.11 (d, JH,H 99.9, 100.2, 100.3, 100.3, 112.3, 112.4, 121.2, 121.3, 121.8, 122.9,
3
= 4.9 Hz, 2 H, Hβ), 9.56 (d, JH,H = 4.7 Hz, 2 H, Hβ), 9.63 (d,
3JH,H = 4.8 Hz, 2 H, Hβ) ppm. 13C NMR (150 MHz, CDCl3): δ =
13.9, 14.0, 22.8, 29.6, 30.1, 30.3, 38.6, 55.7, 110.0, 112.0, 113.4,
134.1, 135.3, 137.1 ppm. UV/Vis (CH2Cl2): λmax (log ε) = 413
126.7, 129.8, 134.3, 134.3, 135.5, 135.6, 140.8, 149.0, 159.6 ppm.
UV/Vis (CH2Cl2): λmax (logε) = 409 (4.77), 475 (4.95), 522 (4.05),
623 (4.22), 719 nm (4.34). HRMS (ESI) m/z calcd. for C97H88N8O3
[M + H]+ 1413.7086; found 1413.7058.
Eur. J. Org. Chem. 2011, 5817–5844
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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