H. Maeda, S. Seki et al.
afford s4 as a white solid (4.33 g, 0.90 mmol, 90%). Rf =0.45 (CHCl3/n-
hexane=1:2); H NMR (600 MHz, CDCl3, 208C): d=6.95 (s, 2H; Ar-H),
(m, 4H; OCH2CH2C14H29), 1.38–1.26 (m, 52H; OC2H4C13H26CH3),
0.88 ppm (t, J=6.6 Hz, 6H; OC15H30CH3); UV/Vis (CH2Cl2): lmax (e)=
432.5 nm (3.7ꢁ104 mꢀ1 cmꢀ1); MALDI-TOF-MS: m/z (%): calcd for
C72H90N4O2: 1042.71 [M]+; found 1042.7 (100), 1043.7 (80), 1044.7 (35).
1
3.98 (t, J=6.6 Hz, 4H; OCH2C15H31), 3.25 (s, 2H; ethynyl-H), 1.81 (quin,
J=6.6 Hz, 4H; OCH2CH2C14H29), 1.45 (m, 4H; OC2H4CH2C13H27), 1.25
(m, 48H; OC3H6C12H24CH3), 0.88 ppm (t, J=6.6 Hz, 6H, OC15H30CH3);
MALDI-TOF-MS: m/z (%): calcd for C42H70O2: 606.54 [M]+; found
606.6 (100), 607.6 (60), 608.6 (20).
4,5-Bis(4-(5,5’-dimethyldipyrrilyl)phenylethynyl)-1,2-dihexadecyloxyben-
zene (2b): Dipyrromethane s6b (162 mg, 0.15 mmol) was dissolved in
THF (10 mL) and stirred in an ice bath. DDQ (74 mg, 0.33 mmol) in
THF (10 mL) was added slowly dropwise over the course of 35 min.
DDQ was removed by alumina column and the solution was evaporated.
The residue was purified by silica gel column chromatography (Wakogel
C-300; EtOAc/n-hexane=3/7) to afford 2b as a yellow solid (22.7 mg,
0.07 mmol, 49%). Rf =0.42 (5% MeOH/CH2Cl2); 1H NMR (600 MHz,
CDCl3, 208C; see also the Supporting Information, Figure S11): d=7.62
(d, J=8.4 Hz, 4H; Ar-H), 7.45 (d, J=8.4 Hz, 4H; Ar-H), 7.06 (s, 2H;
Ar-H), 6.45 (d, J=4.2 Hz, 4H; pyrrole-H), 6.14 (d, J=4.2 Hz, 4H; pyr-
role-H), 4.07 (t, J=6.6 Hz, 4H; OCH2C15H31), 2.48 (s, 12H; CH3), 1.88
(quin, J=6.6 Hz, 4H; OCH2CH2C14H29), 1.50 (m, 4H; OC2H4CH2C13H27),
1.37–1.26 (m, 48H; OC3H6C12H24CH3), 0.88 ppm (t, J=6.6 Hz, 6H;
OC15H30CH3); UV/Vis (CH2Cl2): lmax (e)=445.5 nm (4.9ꢁ104 mꢀ1 cmꢀ1);
MALDI-TOF-MS: m/z (%): calcd for C76H98N4O2: 1098.76 [M]+; found:
1098.8 (100), 1099.7 (80), 1100.7 (20).
4,5-Di(4-formylphenylethynyl)-1,2-dihexadecyloxybenzene (s5): A mix-
ture of 4-bromobenzaldehyde (3.32 g, 17.9 mmol), compound s4 (4.33 g,
7.14 mmol), triethylamine (2 mL), [PdACTHNUTRGNEUNG(PPh3)2Cl2] (150.2 mg, 0.21 mmol),
PPh3 (28.9 mg, 0.11 mmol), and CuI (68.0 mg, 0.35 mmol) in THF
(66 mL) was heated at reflux under nitrogen for 24 h. The reaction mix-
ture was diluted with CH2Cl2 (100 mL), washed with saturated aqueous
NH4Cl (50 mL) and brine (50 mL), and then dried over MgSO4 and
evaporated. The residue was purified by silica gel column chromatogra-
phy (Wakogel C-300; CH2Cl2) and recrystallized from CHCl3/MeOH to
afford s5 as a light yellow solid (2.32 g, 2.92 mmol, 41%). Rf =0.33
(CH2Cl2); 1H NMR (600 MHz, CDCl3, 208C): d=10.02 (s, 2H; CHO),
7.87 (d, J=8.4 Hz, 4H; Ar-H), 7.69 (d, J=8.4 Hz, 4H; Ar-H), 7.05 (s,
2H; Ar-H), 4.06 (t, J=6.6 Hz, 4H; OCH2C15H31), 1.84 (quin, J=6.6 Hz,
4H; OCH2CH2C14H29), 1.46 (m, 4H; OC2H4CH2C13H27), 1.37–1.25 (m,
48H; OC3H6C12H24CH3), 0.88 ppm (t, J=6.6 Hz, 6H; OC15H30CH3);
MALDI-TOF-MS: m/z (%): calcd for C58H78O4: 814.59 [M]+; found:
814.7 (100), 815.8 (60), 816.6 (20).
ACHUTNGERNNUG AHCTUNTGERN(NUGN OAc)2·2H2O (8.34 mg,
[n+n]-Type ZnII complex of 2a, 2an·ZnIIn: Zn
0.038 mmol) was added to dipyrrin 2a (40 mg, 0.038 mmol) in THF
(12 mL) and the solution was stirred for 8 h. The reaction mixture was di-
luted with CHCl3 (40 mL), washed with saturated aqueous Na2CO3
(30 mL) and brine (30 mL), and then dried over MgSO4 and evaporated
4,5-Bis(4-dipyrrolylmethylphenylethynyl)-1,2-dihexadecyloxybenzene
(s6a): TFA (0.05 mL, 0.36 mmol) was added to aldehyde s5 (972 mg,
1.2 mmol), which had been dissolved in pyrrole/CH2Cl2 (15 mL/25 mL)
and degassed by bubbling with nitrogen for 10 min. After the solution
was stirred for 15 min, triethylamine (1 mL) was added. The solvent was
removed by vacuum distillation with gentle heating. The residue was
chromatographed over flash silica gel column (CH2Cl2) and recrystallized
from CHCl3/MeOH to give s6a as a yellow solid (666 mg, 0.64 mmol,
53%). Rf =0.35 (CH2Cl2); 1H NMR (600 MHz, CDCl3, 208C): d=7.95
(brs, 4H; NH), 7.48 (d, J=7.8 Hz, 4H; Ar-H), 7.18 (d, J=8.4 Hz, 4H;
Ar-H), 7.00 (s, 2H; Ar-H), 6.71 (m, 4H; pyrrole-H), 6.17 (m, 4H; pyr-
role-H), 5.91 (br, 4H; pyrrole-H), 5.48 (s, 2H; meso-H), 4.03 (t, J=
6.6 Hz, 4H; OCH2C15H31), 1.85 (quin, J=6.6 Hz, 4H; OCH2CH2C14H29),
1.47 (m, 4H; OC2H4CH2C13H27), 1.36–1.21 (m, 48H; OC3H6C12H24CH3),
0.88 ppm (t, J=6.6 Hz, 6H; OC15H30CH3); MALDI-TOF-MS: m/z (%):
calcd for C72H94N4O2: 1046.74 [M]ꢀ; found: 1046.7 (100), 1047.7 (34),
1048.7 (35).
to afford 2an·ZnII (n=2 and 3 as a mixture) as an orange solid. See the
n
details in the 1H NMR spectra (600 MHz, CDCl3, 208C; the Supporting
Information, Figure S12) and FT-ICR-MS (the Supporting Information,
Figure S12); elemental analysis calcd (%) for (C72H88N4O2Zn)n: C 78.13,
H 8.01, N 5.06; found: C 78.26, H 8.13, N 5.04.
[2+2]-Type ZnII complex of 2b, 2b2·ZnII
2
0.010 mmol) was added to dipyrrin 2b (10 mg, 0.010 mmol) in THF
(3.3 mL) and the solution was stirred for 6 h. The reaction mixture was
diluted with CHCl3 (20 mL), washed with saturated aqueous Na2CO3
(20 mL) and brine (20 mL), and then dried over MgSO4 and evaporated.
The residue was purified by GPC column with toluene and by GPC-
HPLC, and recrystallized from CHCl3/MeOH to afford 2b2·ZnII as an
2
orange solid (4.1 mg, 1.8 mmmol, 36%). Higher oligomers were also ob-
tained (see also the Supporting Information, Figure S13a). Rf =0.45
(CH2Cl2/n-hexane=1:1); m.p. 2358C (decomp); 1H NMR (600 MHz,
CDCl3, 208C; see also the Supporting Information, Figure S14): d=7.53
(d, J=7.8 Hz, 8H; Ar-H), 7.35 (d, J=7.8 Hz, 8H; Ar-H), 7.07 (s, 4H;
Ar-H), 6.47 (d, J=4.2 Hz, 8H; pyrrole-H), 5.92 (d, J=4.2 Hz, 8H; pyr-
role-H), 4.08 (t, J=6.6 Hz, 8H; OCH2C15H31), 1.94 (s, 24H; CH3), 1.87
(quin, J=7.2 Hz, 8H; OCH2CH2C14H29), 1.50 (m, 8H; OC2H4CH2C13H27),
1.39–1.25 (m, 96H; OC3H6C12H24CH3), 0.88 ppm (t, J=6.6 Hz, 12H;
OC15H30CH3); UV/Vis (CH2Cl2): lmax (e)=513 nm (16ꢁ104 mꢀ1 cmꢀ1); FT-
ICR-MS (MALDI): m/z (%): calcd for C152H192N8O4Zn2: 2321.36 [M]+;
found 2321.3 (32), 2322.3 (54), 2323.3 (68), 2324.3 (75), 2325.3 (100),
2326.3 (93), 2327.3 (80), 2328.3 (60), 2329.3 (45), 2330.3 (28), 2331.3 (14),
2332.3 (9); elemental analysis calcd (%) for C152H192N8O4Zn2: C 78.49, H
8.32, N 4.82; found: C 78.25, H 8.44, N 4.62.
4,5-BisACHTUNGTRENNUNG(4-di(5-methylpyrrol-2-yl)methylphenylethynyl)-1,2-dihexadecylox-
ybenzene (s6b): TFA (0.005 mL, 0.07 mmol) was added to aldehyde s5
(200 mg, 0.25 mmol) and 2-methylpyrrole (101 mg, 1.25 mmol) dissolved
in CH2Cl2 (20 mL). After the solution was stirred for 15 min, triethyla-
mine (1 mL) was added and the solution was evaporated. The residue
was purified by silica gel column chromatography (Wakogel C-300;
CH2Cl2/n-hexane=2/1) to give s6b as a yellow solid (162 mg, 0.15 mmol,
59%). Rf =0.58 (CH2Cl2); 1H NMR (600 MHz, CDCl3, 208C): d=7.62
(brs, 4H; NH), 7.48 (d, J=8.4 Hz, 4H; Ar-H), 7.19 (d, J=8.4 Hz, 4H;
Ar-H), 7.01 (s, 2H; Ar-H), 5.79 (m, 4H; pyrrole-H), 5.76 (m, 4H; pyr-
role-H), 5.36 (s, 2H; meso-H), 4.03 (t, J=6.6 Hz, 4H; OCH2C15H31), 2.21
(s, 12H; CH3), 1.84 (quin, J=6.6 Hz, 4H; OCH2CH2C14H29), 1.46 (m,
4H; OC2H4CH2C13H27), 1.37–1.26 (m, 48H; OC3H6C12H24CH3), 0.88 ppm
(t, J=6.6 Hz, 6H; OC15H30CH3); MALDI-TOF-MS: m/z (%): calcd for
C76H102N4O2: 1102.80 [M]+; found: 1102.8 (100), 1103.7 (58).
[3+3]-Type ZnII complex of 2b, 2b3·ZnII
3
0.010 mmol) was added to dipyrrin 2b (10 mg, 0.010 mmol) in THF
(3.3 mL) and the solution was stirred for 6 h. After this time, the reaction
mixture was diluted with CHCl3 (20 mL), washed with saturated aqueous
Na2CO3 (20 mL) and brine (20 mL), and then dried over MgSO4 and
evaporated. The residue was purified by GPC column with toluene and
4,5-Bis(4-dipyrrilylphenylethynyl)-1,2-dihexadecyloxybenzene (2a): Di-
pyrromethane s6a (666 mg, 0.63 mmol) was dissolved in THF (40 mL)
and stirred in an ice bath. DDQ (317 mg, 1.4 mmol) in THF (30 mL) was
added slowly dropwise over the course of 35 min. DDQ was removed by
alumina column and the solution was evaporated. The residue was puri-
fied by silica gel column chromatography (Wakogel C-300; 3% MeOH/
CH2Cl2) and GPC column with THF to afford 2a as a yellow solid
(430 mg, 0.41 mmol, 65%). Rf =0.38 (3% MeOH/CH2Cl2); 1H NMR
(600 MHz, CDCl3, 208C; see also the Supporting Information, Fig-
ure S10): d=7.65–7.64 (m, 8H; Ar-H and pyrrole-H), 7.49 (d, J=8.4 Hz,
4H; Ar-H), 7.08 (s, 2H; Ar-H), 6.60 (d, J=3.6 Hz, 4H; pyrrole-H), 6.38
(d, J=4.2 Hz, 4H; pyrrole-H), 4.06 (t, J=6.6 Hz, 4H; OCH2C15H31), 1.88
by GPC-HPLC, and recrystallized from CHCl3/MeOH to afford 2b3·ZnII
3
as an orange solid (3.1 mg, 0.9 mmmol, 27%). Higher oligomers were also
obtained (see the Supporting Information, Figure S13a). Rf =0.50
(CH2Cl2/n-hexane=1:1); m.p. 1308C (c.p. 2308C); 1H NMR (600 MHz,
CDCl3, 208C; see also the Supporting Information, Figure S16): d=7.66
(d, J=8.4 Hz, 12H; Ar-H), 7.51 (d, J=8.4 Hz, 12H; Ar-H), 7.09 (s, 6H;
Ar-H), 6.57 (d, J=3.6 Hz, 12H; pyrrole-H), 6.18 (d, J=4.2 Hz, 12H;
pyrrole-H), 4.08 (t, J=6.6 Hz, 12H; OCH2C15H31), 2.08 (s, 36H; CH3),
1.89 (quin, J=7.2 Hz, 12H; OCH2CH2C14H29), 1.51 (m, 12H;
11682
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 11676 – 11685