11708 J. Phys. Chem., Vol. 100, No. 28, 1996
Toupance et al.
1370, 1351, 1327, 1296, 1252 (val. asym. Car-O-Cal), 1203,
1126 (val. asym. Cal-O-Cal), 1055 (val. sym. Car-O-Cal), 928,
OCH3), 231 (M+ - CH2OCH3), 218 (MH+ - CH2CH2OCH3),
201 (MH+ - (CH2CH2OCH3) - (CH3)), 186 (M+ - (CH2-
CH2OCH3) - (OCH3)), 171 (MH+ - (CH2CH2OCH3) - (CH2-
OCH3)). 1H (300 MHz, CDCl3) δ ppm: 3.42 (s, 6H, OCH3),
3.78 (t, 4H, J ) 4.51 Hz), 4.22 (t, 4H, J ) 4.60 Hz), 7.30 (s,
2H, aromatic protons). 13C (75 MHz, CDCl3) δ ppm: 59.14,
69.22, 70.39, 108.67, 115.71, 116.75, 152.27. IR (KBr): 3061,
2991, 2930, 2815, 2228 (CdN), 1588, 1566, 1525, 1448, 1404,
1366, 1296 (val. asym. Car-O-Cal), 1230, 1132 (val. asym.
864, 652 (C-Br) cm-1
.
1,2-Bis(12-methoxy-1,4,7,10-tetraoxadodecanyl)-4,5-dicy-
anobenzene, 5d. A mixture of 5 g (7.71 mmol) of 4d, 2.07 g
(23.1 mmol) of CuCN, and 39 mL of freshly distilled DMF
was refluxed under nitrogen for 8 h. After cooling and
evaporation of the solvent, the crude product, dissolved in
dichloromethane, was treated with 200 mL of aqueous NH4OH
(25%); air was then passed through the solution for 24 h. The
aqueous solution became dark blue. A similar treatment was
made with 200 mL of ethylene diamine (25%). The organic
layer was washed with distilled water, dried (MgSO4), filtered,
and concentrated under reduced pressure. The green-brownish
oil was chromatographed on silica gel (elution gradient: CH2-
Cl2/ethyl acetate/EtOH from 100:0:0 to 70:26:4 (v/v)), and a
colorless oil was obtained in 61% yield (2.7 g). Rf ) 0.45 (SiO2,
CH2Cl2/ethyl acetate/EtOH, 70:26:4 (v/v)).
Cal-O-Cal), 1085 (val. sym. Car-O-Cal), 891 cm-1
.
Bis[4,5,4′,5′,4′′,5′′,4′′′,5′′′-octakis(12-methoxy-1,4,7,10-tet-
raoxadodecanyl)phthalocyanine] Lutetium(III), 1d. A round-
bottomed flask fitted with a condenser was degassed and flame-
dried under dry argon. The flask was charged under argon with
the dinitrile derivative 5d (1 g, 1.85 mmol), Lu(OAc)3‚3H2O
(81.5 mg, 0.231 mmol), 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU) (185 µL, 1.23 mmol), and 4.5 mL of hexan-1-ol; the
mixture was refluxed for 8 h. The crude product was deposited
on Celite and successively washed with cooled and warmed
n-heptane (500 mL) and finally with a mixture of n-heptane:
CH2Cl2 (20:1, v/v) (200 mL). The remaining solids were put
in a thimble of a Soxhlet apparatus and extracted with n-heptane
for 3 days to remove organic impurities. Phthalocyanines were
recovered by extracting the solid residue with chloroform.
Purification was achieved by (i) column chromatography over
silica gel (CHCl3/ethylacetate/EtOH, 80:15:5 (v/v)), then CHCl3/
MeOH, 95:5 (v/v); (ii) two successive preparative thin layer
chromatographies (neutral alumina; eluent CHCl3/ethylacetate/
propan-2-ol, 60:37:3 (v/v); Rf ) 0.41). A precipitation from a
CH2Cl2/n-heptane (1:5 (v/v)) mixture led to 70 mg (yield: 6.5%)
of a viscous paste.
Elemental analysis for C26H40O10N2 (Mw ) 540). Calc: C,
57.76; H, 7.46; N, 5.18. Found: C, 56.82; H, 7.66; N, 4.91.
Mass spectrometry (GCMS) m/z: 495 (M+ - CH2OCH3), 451
(M+ - CH2OCH2CH2OCH3), 407 (M+ - CH2(OCH2CH2)2-
OCH3), 363 (M+ - CH2(OCH2CH2)3OCH3), 171 (MH+
-
((OC2H4)4OMe) - ((C2H4O)3OMe)). 1H (300 MHz, CDCl3) δ
ppm: 3.32 (s, 6H, OCH3), 3.49 (t, 4H, J ) 4.59 Hz), 3.60 (m,
20H), 3.84 (t, 4H, J ) 4.59 Hz), 4.21 (t, 4H, J ) 4.6 Hz), 7.23
(s, 2H, aromatic protons). 13C (75 MHz, CDCl3) δ ppm: 58.78,
69.13, 69.22, 70.25, 70.35, 70.37, 70.41, 70.74, 71.68, 108.49,
115.63, 116.85, 152.18. IR (KBr): 3056, 2876, 2229 (CtN),
1590, 1563, 1518, 1452, 1408, 1351, 1290 (val. asym. Car-
O-Cal), 1230, 1108 (val. asym. Cal-O-Cal), 1040 (val. sym.
Car-O-Cal), 949, 890 cm-1
.
Elemental analysis for C208H320O80N16Lu (Mw ) 4500).
Calc: C, 55.52; H, 7.17; N, 4.98; Lu, 3.89. Found: C, 55.16;
H, 7.21; N, 4.88; Lu, 4.06. IR (KBr): 2879, 1599, 1500, 1458,
1363, 1277, 1200, 1107, 1062, 948, 858 cm-1. UV-visible
(CHCl3): ꢀ292 102 000, ꢀ367 144 000, ꢀ475 41 000, ꢀ602 32 000,
ꢀ666 180 000.
Bis[4,5,4′,5′,4′′,5′′,4′′′,5′′′-octakis(6-methoxy-1,4-dioxahexyl)-
phthalocyanine] Lutetium(III), 1b. The same procedure as for
1d, was used. Quantities: 1 g (2.74 mmol) of 5b, 120.6 mg
(0.343 mmol) of Lu(OAc)3‚3H2O, 205 µL (1.37 mmol) of DBU
in hexan-1-ol (7 mL), reflux for 18 h. Purification: column
chromatography on silica gel (elution gradient CHCl3/EtOH
from 100:0 to 90:10 (v/v)), preparative thin layer chromatog-
raphy (neutral alumina; eluent CHCl3/ethylacetate/propan-2-ol,
60:36.5:3.5 (v/v); Rf ) 0.5), and reprecipitation in a CH2Cl2/
n-heptane (2:5) mixture. Yield: 67 mg (6%), green powder,
mp ) 138 °C.
1,2-Bis(6-methoxy-1,4-dioxahexyl)-4,5-dicyanobenzene, 5b.
The same procedure as for 5d was used. Quantities: 8 g (0.017
mol) of 4b, 4.54 g (0.051 mol) of CuCN in DMF (70 mL), reflux
for 6 h. Purification: column chromatography on silica gel
(elution gradient: CH2Cl2/ethylacetate from 100:0 to 80:20, then
CH2Cl2/EtOH from 98:2 to 80:20 (v/v) and recrystallization in
a toluene/n-heptane (2:1 v/v) mixture. Yield: 3.23 g (55%),
white crystals. Rf ) 0.30 (SiO2, CH2Cl2/EtOH, 97:3 v/v).
Elemental analysis for C18H24O6N2 (Mw ) 364). Calc: C,
59.33; H, 6.64; N, 7.69. Found: C, 59.02; H, 6.61; N, 7.55.
Mass spectrometry (GCMS) m/z: 364 (M+), 306 (MH+ - CH2-
CH2OCH3), 262 (MH+ - (CH2CH2O)2CH3), 186 (M+ - OCH2-
CH2OCH3 - (CH2CH2O)2CH3), 171 (M+ - (OCH2CH2OCH3)
- (O(CH2CH2O)2CH3)). 1H (300 MHz, CDCl3) δ ppm: 3.42
(s, 6H, OCH3), 3.59 (t, 4H, J ) 4.53 Hz), 3.75 (t, 4H, J ) 4.54
Hz), 3.94 (t, 4H, J ) 4.64 Hz), 4.30 (t, 4H, J ) 4.64 Hz), 7.30
(s, 2H, aromatic protons). 13C (75 MHz, CDCl3) δ ppm: 58.92,
69.19, 69.31, 70.76, 71.76, 108.60, 115.67, 116.95, 152.25. IR
(KBr): 3060, 2940, 2884, 2228 (CdN), 1588, 1566, 1525, 1456,
1408, 1354, 1294 (val. asym. Car-O-Cal), 1232, 1144, 1124,
1107 (val. asym. Cal-O-C1l), 1088, 1048 (val. sym. Car-O-
Elemental analysis for C144H192O48N16Lu (Mw ) 3090).
Calc: C, 55.97; H, 6.26; N, 7.26; Lu, 5.66. Found: C, 55.58;
H, 6.20; N, 7.11; Lu, 5.55. IR (KBr): 3071, 2924, 2875, 1597,
1500, 1451, 1386, 1354, 1322, 1278, 1204, 1124, 1063, 938,
859, 757 cm-1
149 000, ꢀ475 42 000, ꢀ602 32 000, ꢀ665 185 000.
. UV-visible (CHCl3): ꢀ291 109 000, ꢀ367
Cal), 955, 890 cm-1
.
1,2-Bis(3-methoxy-1-oxapropyl)-4,5-dicyanobenzene, 5a. The
same procedure as for 5d was used. Quantities: 10 g (0.026
mol) of 4a , 7 g (0.078 mol) of CuCN in DMF (131 mL), reflux
for 8 h. Purification: column chromatography on silica gel
(elution gradient: CH2Cl2/ethylacetate from 100:0 to 8:2, v/v)
and recrystallization in a toluene/n-heptane (10:0.5 v/v) mixture.
Yield: 4.72 g (66%), white crystals. Rf ) 0.43 (SiO2, CH2-
Cl2/ethylacetate, 8:2 (v/v)).
Bis[4,5,4′,5′,4′′,5′′,4′′′,5′′′-octakis(3-methoxy-1-oxapropyl)-
phthalocyanine] Lutetium(III), 1a. The same procedure as for
1d was used. Quantities: 1 g (3.61 mmol) of 5a, 159 mg (0.452
mmol) of Lu(OAc)3‚3H2O, 270 µL (1.81 mmol) of DBU, hexan-
1-ol (12 ml), reflux for 22 h. Purification: column chroma-
tography on silica gel (elution gradient CHCl3/EtOH from 100:0
to 96:4 (v/v)), preparative thin layer chromatography (neutral
alumina; eluent CHCl3/ethylacetate/propan-2-ol, 60:36:3 (v/v/
v); Rf ) 0.6), and reprecipitation in a CH2Cl2/n-heptane (2:3)
mixture. Yield: 116 mg (12%), green powder. mp ) 246 °C.
Elemental analysis for C14H16O4N2 (Mw ) 276). Calc: C,
60.86; H, 5.84; N, 10.14. Found: C, 60.79; H. 5.74; N, 10.04.
Mass spectrometry (GCMS) m/z: 276 (M+), 244 (MH+
-
Elemental analysis for C112H128O32N16Lu (Mw ) 2385).