Pentaerythritol-Bridged Cofacial Bismetallophthalocyanines
FULL PAPER
UV-1601 UV/Vis spectrophotometer, respectively. Elemental analy-
ses were performed with the LECO CHNS 932. H NMR spectra
[M + 3Na]+. C112H80Co2N16O16: calcd. C 66.47, H 3.98, N 11.07;
found C 67.14, H 4.11, N 11.32.
1
were obtained with a Varian Mercury-Vx 400 MHz spectrometer.
Mass spectra were acquired with a Voyager-DETM PRO MALDI-
TOF mass spectrometer (Applied Biosystems, USA) equipped with
a nitrogen UV-Laser operating at 337 nm. Spectra were recorded
in linear mode with an average of 50 shots. 3-Indole acrylic acid
(IAA) (20 mg/mL in acetonitrile) MALDI matrix for 4 and 5, and
α-cyano-4-hydroxycinnamic acid (ACCA) (15 mg/mL in 1:1 water/
acetonitrile) MALDI matrix for 6 and 7 were prepared. MALDI
samples were prepared by mixing the complex (2 mg/mL in di-
methyl sulfoxide) with the matrix solution (1:10, v/v) in a 0.5-mL
Eppendorf® microtube. Finally this mixture (1 µL) was deposited
on the sample plate, dried at room temp. and then analyzed. The
potassium, zinc, and cobalt contents in the digested mixtures were
determined using external standards with an Agilent 7500a induc-
tively coupled plasma mass spectrometer (ICP-MS). For the ICP-
MS measurements, compounds 8 and 9 (10 mg) were digested by a
mixture of acids (HNO3/HClO4/HF, 8:2:2, v/v) at 170 °C for 1 h.
2Ј,10Ј,16Ј,24Ј-[Tetrakis(4,4Ј-2,2-bis(hydroxymethyl)propane-1,3-
diyl)bis(oxy)]bis(phthalocyaninato)dizinc(II) (6) and 2Ј,10Ј,16Ј,24Ј-
[Tetrakis(4,4Ј-2,2-bis(hydroxymethyl)propane-1,3-diyl)bis(oxy)]bis-
(phthalocyaninato)dicobalt(II) (7): A suspension of 4 (0.11 g,
0.06 mmol) or 5 (0.12 g, 0.054 mmol) and Pd/C(10%) (30 mg) in
DMSO (20 mL) was hydrogenated at room temp. under 1 atm hy-
drogen pressure for 8 h. The catalyst was filtered off, and the mix-
ture was precipitated with the addition of ethanol to give 6 or 7.
Compounds 6 or 7 were dissolved in DMF (2 mL) and reprecipi-
tated with a mixture of acetone/ethanol (1:1, v/v). After filtration,
the precipitates were washed successively with hot acetic acid,
water, and alcohol, and dried in vacuo. The purification of 6 and
7 was carried out using silica gel columns with a THF/DMF system
changing from 10:0.1 to 10:1 (v/v). These compounds are soluble
in THF, DMSO, DMF, and DMA. Yield (6): 69 mg (76%). M.p.
Ͼ300 °C. UV/Vis (DMF): λ (log ε) = 680 (5.08), 639 (5.02), 344
1
(5.11) nm (Figure 1). H NMR ([D6]DMSO): δ = 11.35 (br s, 8 H,
4,4Ј-(2-Phenyl-1,3-dioxane-5,5-diyl)bis(methylene)bis(oxy)diphthalo-
nitrile (3): A mixture of 1 (1.79 g, 8 mmol), 2 (2.77 g, 16 mmol),
and K2CO3 (6.62 g, 48 mmol) in DMF (80 mL) was heated with
stirring at 50 °C under argon for 30 h. The cooled reaction mixture
was poured into cold water (100 mL) with stirring. The formed
precipitate was filtered, washed with water, and dried in vacuo. The
separation of the prepared compounds was achieved by column
chromatography using silica gel with CHCl3. The white powder
product was obtained by evaporation of the solvent. This com-
pound is readily soluble in CHCl3, CH2Cl2, acetone, and THF.
Yield 1.82 g (48%). M.p. 223 °C. 1H NMR (CDCl3): δ = 7.73–7.21
(m, 11 H, arom. CH), 5.51 (s, 1 H, acetal CH), 4.88–3.64 (m, 8 H,
aliph. OH, disappeared with D2O exchange), 8.31–6.94 (m, 24 H,
arom. CH), 4.12–3.13 (m, 32 H, aliph. CH ) ppm. IR (KBr): ν =
˜
2
3402 (aliph. OH), 3059 (arom. CH), 2926–2851 (aliph. CH), 1603
(arom. C=C), 1466, 1228 (aliph.–O–arom.), 1089, 1045 cm–1
.
MALDI-TOF MS: m/z = 1685 [M + H]+, 1596 [M – 88]+ (Fig-
ure 4). C84H64N16O16Zn2: calcd. C 59.90, H 3.83, N 13.31; found
C 60.44, H 3.79, N 13.63. Yield (7): 62 mg (63%). M.p. Ͼ300 °C.
UV/Vis (DMF): λ (log ε) = 674 (5.13), 610 (4.69), 336 (4.88) nm
(Figure 1). IR (KBr): ν = 3396 (aliph. OH), 3053 (arom. CH),
˜
2933–2874 (aliph. CH), 1603 (arom. C=C), 1468, 1232 (aliph.–O–
arom.), 1094, 1056 cm–1. MALDI-TOF MS: m/z = 1672 [M +
H]+ (Figure 5). C84H64Co2N16O16: calcd. C 60.36, H 3.86, N 13.41;
found C 61.01, H 3.80, N 13.11.
aliph. CH ) ppm. IR (KBr): ν = 3074–3038 (arom. CH), 2926–2851
˜
2
(aliph. CH), 2231 (CϵN), 1595 (arom. C=C), 1483, 1390, 1309,
1246 (aliph.–O–arom.), 1165, 1093 cm–1. C28H20N4O4: calcd. C
70.58, H 4.23, N 11.76; found C 70.81, H 4.29, N 11.62.
2Ј,10Ј,16Ј,24Ј-[{Tetrakis(4,4Ј-2,2-bis(oxidomethyl)propane-1,3-diyl)-
bis(oxy)}]bis(phthalocyaninato)dizinc(II)] Octapotassium (8) and
2Ј,10Ј,16Ј,24Ј-[{Tetrakis(4,4Ј-2,2-bis(oxidomethyl)propane-1,3-diyl)-
bis(oxy)}]bis(phthalocyaninato)dicobalt(II)] Octapotassium (9):
Compound 6 (0.034 g, 0.02 mmol) or 7 (0.017 g, 0.01 mmol) was
suspended in aqueous KOH solution (20%, 5 mL) and boiled for
10 min. The solution of the compound 8 or 9 was cooled, and the
mixture was poured into ethanol (100 mL). The formed precipitate
was filtered off, dissolved in water and reprecipitated in ethanol
several times until the solution was neutral. The products were then
washed with ethanol and diethyl ether, and dried in vacuo. Both
compounds are soluble in water at room temp. Yield (8): 0.031 g
(77%). M.p. Ͼ300 °C. UV/Vis (water): λ (log ε) = 687 (4.62), 637
2Ј,10Ј,16Ј,24Ј-[Tetrakis(2-phenyl-1,3-dioxan-5,5-diyl)bis(methylene)-
bis(oxy)]bis(phthalocyaninato)dizinc(II) (4) and 2Ј,10Ј,16Ј,24Ј-[Tet-
rakis(2-phenyl-1,3-dioxan-5,5-diyl)bis(methylene)bis(oxy)]bis-
(phthalocyaninato)dicobalt(II) (5): Compound 3 (0.24 g, 0.5 mmol)
and Zn(OAc)2·2H2O (0.22 g, 1 mmol) or Co(OAc)2·4H2O (0.13 g,
0.5 mmol) were ground in a mortar. Then the mixture was put in
a glass tube, and the tube was purged with argon. After being se-
aled, the mixture was heated at 300 °C for 10 min. After cooling to
room temp., the deep turquoise blue 4 or deep blue 5 were pow-
dered by grinding. The crude products were dissolved in DMF
(5 mL) and reprecipitated with a mixture of acetone/ethanol (1:1,
v/v). After filtration, the precipitates were washed successively with
hot water, ethanol, and acetone, and dried in vacuo. Compounds
4 and 5 were isolated using silica gel and a gradient of THF/DMF
(10:0.1 to 10:2, v/v) as the eluent. These compounds are soluble
in THF, DMSO, DMF, and DMA. Yield (4): 58 mg (23%). M.p.
Ͼ300 °C. UV/Vis (DMF): λ (log ε) = 680 (5.29), 638 (4.92), 353
(5.12) nm (Figure 1). 1H NMR ([D6]DMSO): δ = 8.42–7.03 (m, 44
H, arom. CH), 6.14 (s, 4 H, acetal CH), 4.81–3.57 (m, 32 H, aliph.
(4.70), 338 (4.53) nm (Figure 2). IR (KBr): ν = 3061 (arom. CH),
˜
2939–2870 (aliph. CH), 1605 (arom. C=C), 1489, 1226 (aliph.–O–
arom.), 1095, 1044 cm–1. C84H56N16O16K8Zn2: calcd. C 50.72, H
2.84, N 11.27; found C 51.08, H 2.79, N 11.31. ICP-MS (Zn, K):
Anal. calcd. for C84H56N16O16K8Zn2: Zn 6.58, K 15.73; found Zn
6.47, K 15.91. Yield (9): 0.013 g (65 %). M.p. Ͼ300 °C. UV/Vis
(Water): λ (log ε) = 685 (4.36), 623 (4.47), 279 (4.67) nm (Figure 3).
IR (KBr): ν = 3067 (arom. CH), 2931–2865 (aliph. CH), 1601
˜
(arom. C=C), 1482, 1224 (aliph.–O–arom.), 1093, 1047 cm–1
.
CH ) ppm. IR (KBr): ν = 3067 (arom. CH), 2926 (aliph. CH), 1607
˜
2
C84H56Co2N16O16K8: calcd. C 51.06, H 2.86, N 11.34; found C
50.81, H 2.79, N 11.18. ICP-MS (Co, K): Anal. calcd. for
C84H56Co2N16O16K8: Co 5.96, K 15.83; found Co 6.07, K 15.79.
(arom. C=C), 1232 (aliph.–O–arom.), 1090, 1065 cm–1. MALDI-
TOF MS: m/z = 2038 [M + H]+ , 2082 [M – H + 2Na]+ .
C112H80N16O16Zn2: calcd. C 66.05, H 3.96, N 11.00; found C 65.84,
H 3.89, N 11.12. Yield (5): 46 mg (18%). M.p. Ͼ300 °C. UV/Vis Electrochemistry and Spectroelectrochemistry: The cyclic voltam-
(DMF): λ (log ε) = 665 (5.03), 625 (4.88), 330 (5.10), 278 (4.99) nm metry (CV) and controlled potential coulometry (CPC) measure-
(Figure 1). IR (KBr): ν = 3045 (arom. CH), 2941–2850 (aliph. CH), ments were carried out with a Princeton Applied Research Model
˜
1603 (arom. C=C), 1265, 1228 (aliph.–O–arom.), 1095, 1057 cm–1. VersaStat II potentiostat/galvanostat, which was controlled by an
MALDI-TOF MS: m/z = 2023 [M + H]+, 2045 [M + Na]+, 2091
external PC and utilized a three-electrode configuration at 25 °C.
Eur. J. Inorg. Chem. 2007, 3519–3526
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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