8124 Inorganic Chemistry, Vol. 48, No. 17, 2009
Dumur et al.
127.6, 129.8, 130.3, 136.1, 137.5, 138.3, 143.1, 143.8, 148.6,
149.2, 152.4, 154.6, 155.3, 155.7. UV-visible (CH3CN) [λmax
(nm); (εmax) (M-1 cm-1)]: 485 (65370), 274 (35410) . ESI Mass
Spectrum (m/z) (positive mode): 391.9 ([C53H49N7]2+/2); Anal.
Found: C, 59.34; H, 4.73; N, 9.17; P, 5.71; F, 21.18. Calcd for
C53H49N7P2F12 (%): C, 59.27; H, 4.60; N, 9.13; P, 5.77; F, 21.23.
salts) was isolated as a dark-red solid by precipitation with
a concentrated solution of NH4PF6, washed with ethanol (2 ꢀ
10 mL), and dried with diethyl ether (2 ꢀ 10 mL). (Yield,
0.091 g, 51%).
1H NMR (DMSO-d6), δ ppm: 9.48 (s, 4H), 9.07 (d, 4H, 3J =
8.3 Hz), 9.00 (d, 4H, 3J = 6.7 Hz), 8.50 (d, 4H, 3J = 8.1 Hz), 8.16
(d, 4H, 3J = 6.6 Hz), 8.10 (t, 4H, 3J = 7.5 Hz), 7.99 (d, 4H, 3J =
L2 Cl2. The chloride salt of L2 was prepared by addition of
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16 Hz), 7.91 (d, 4H, J = 8.1 Hz), 7.63 (d, 4H, J = 8.7 Hz),
7.52 (d, 4H, 3J = 8.9 Hz), 7.28 (dd, 4H, 3J = 6.2 Hz), 6.81 (d,
4H, 3J = 9 Hz), 5.84 (s, 4H, -CH2-py+), 3.04 (s, 12H, N-CH3).
UV-visible (CH3CN) [λmax (nm); (εmax) (M-1 cm-1)]: 493
(71780), 310 (56140), 282 (65610). ESI Mass Spectrum (m/z)
(positive mode): 298.9 ([M]4+/4), 446.6 ([M+PF6]3+/3), 742.3
([M+2PF6]2+/2). Anal. Found: C, 49.96; H, 3.59; N, 7.73; Ru,
5.55; P, 7.12; F, 26.41. Calcd for C74H64N10RuP4F24 (%):
C, 50.09; H, 3.64; N, 7.89; Ru, 5.70; P, 6.98; F, 25.70.
tetrabutylammonium chloride to a solution of L2 (PF6)2 in
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acetone. L2 Cl2 precipitated and was recovered by filtration,
dried with diethyl ether, and used without further purification.
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5,50-Di([4-dimethylaminostyryl-4-pyridiniumyl]methyl)-2,20-
bipyridine hexafluorophosphate (L3 (PF6)2). Ligand L3 was
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synthesized and purified according to the procedure used for
L2 starting from DASpyr (0.905 g, 4 mmol) and bpy-(CH2Br)2
(684 mg, 2 mmol) (Yield, 1.7 g, 93%).
1H NMR (DMSO-d6), δ ppm: 8.96 (d, 4H, 3J = 6.55 Hz), 8.90
(d, 2H, 3J = 1.3 Hz), 8.44 (d, 2H, 3J = 8.9 Hz), 8.10 (d, 4H, 3J =
6.55 Hz), 8.08 (d, 2H, 3J = 1.3 Hz), 7.96 (d, 2H, 3J = 16 Hz),
7.60 (d, 4H, 3J = 8.9 Hz), 7.20 (d, 2H, 3J = 16 Hz), 6.79 (d, 4H,
3J = 8.9 Hz), 5.81 (s, 4H, -CH2-py+), 3.02 (s, 12H, N-CH3).
13C NMR (75.47 MHz, DMSO-d6), δ ppm: 39.7, 58.9, 111.9,
116.9, 118.2, 120.8, 122.3, 122.7, 124.7, 127.8, 129.2, 130.4,
136.2, 137.7, 138.0, 142.8, 143.6, 148.8, 149.6, 152.0, 154.4,
154.9, 156.1. UV-visible (CH3CN) [λmax (nm); (εmax) (M-1
cm-1)]: 486 (78120), 287 (29510). ESI Mass Spectrum (m/z)
(positive mode): 315.5 ([C42H42N6]2+/2). Anal. Found: C,
54.68; H, 4.57; N, 9.06; P, 6.92; F, 24.85. Calcd for
C42H42N6P2F12 (%): C, 54.79; H, 4.60; N, 9.13; P, 6.73; F, 24.76.
[Ru(L1)Cl3] Cl. RuCl3 3H20 (0.785 g, 3 mmol) was dissolved
[Zn(L1)2] (PF6)4 - (Zn-1). Zn-1 was synthesized and purified
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following the procedure described for Ru-1, starting from
[Zn(L1)Cl3] (0.072 g, 0.1 mmol) and L1 Br (0.063 g, 0.1 mmol).
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(Yield, 141 mg, 81%).
1H NMR (DMSO-d6), δ ppm: 9.37 (s, 4H), 9.10 (d, 4H, 3J =
7.7 Hz), 8.98 (d, 4H, 3J = 6.2 Hz), 8.47 (d, 4H, 3J = 7.7 Hz), 8.28
(d, 4H, 3J = 6.9 Hz), 8.14 (d, 4H, 3J = 6.9 Hz), 8.00 (d, 2H, 3J =
15.4 Hz), 7.94-7.88 (m, 8H), 7.62 (d, 4H, 3J = 9.2 Hz), 7.49 (d,
4H, 3J = 6.9 Hz), 7.22 (d, 2H, 3J = 15.4 Hz), 6.80 (d, 4H, 3J =
9.2 Hz), 5.83 (s, 4H, -CH2-py+), 3.03 (s, 12H, N-CH3). UV-
visible (CH3CN) [λmax (nm); (εmax) (M-1 cm-1)]: 487 (83130),
285 (80080). ESI Mass Spectrum (m/z) (positive mode): 289.4
([M]4+/4), 434 ([M+PF6]3+/3), 724.3 ([M+2PF6]2+/2). Anal.
Found: C, 51.03; H, 3.62; N, 7.99; Zn, 3.58; P, 7.24; F, 26.36.
Calcd for C74H64N10ZnP4F24 (%): C, 51.12; H, 3.71; N, 8.06;
Zn, 3.76; P, 7.13; F, 26.23.
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in ethanol (45 mL). A solution of L1 Br (0.941 g, 1.5 mmol) in
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ethanol (40 mL) was added dropwise, and the mixture was
stirred at reflux for one night. The resulting mixture was filtrated
while hot. The precipitate was vigorously washed with water (3
ꢀ 20 mL), ethanol (1 ꢀ 20 mL), and diethyl ether (2 ꢀ 20 mL).
[Ru(tpy-NMe2)(L1)] (PF6)3 - (Ru-10). [Ru(L1)Cl3] Cl (0.079
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g, 0.1 mmol) and tpy-NMe2 (0.036 g, 0.1 mmol) were refluxed
for one night in a mixture of EtOH/H2O/DMF (45/15/3 mL).
After cooling, an aqueous solution of NH4PF6 (200 mg, 5 mL)
was added. The resulting mixture was concentrated under
vacuum to about 25 and 80 mL of water were added. The
dark-red solid obtained was filtered, washed successively with
water (3 ꢀ 10 mL), ethanol (3 ꢀ 10 mL) and diethyl ether (3 ꢀ
10 mL). Slow diffusion of ether onto a solution of Ru-10 in
acetonitrile produced a precipitate, which was collected by
filtration (Yield, 0.102 g, 71%).
[Ru(L1)Cl3] Cl was dried overnight in a vacuum desiccator over
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P2O5 (Yield, 1.14 g, 96%).
Anal. Found: C, 56.13; H, 4.01; N, 8.69; Cl, 18.11; Ru, 12.64.
Calcd for C37H32Cl4N5Ru (%): C, 56.28; H, 4.09; N, 8.87; Cl,
17.96; Ru, 12.80.
[Ru(L2)Cl3] Cl2. [Ru(L2)Cl3] Cl2 was synthesized accor-
ding to the above-described procedure for [Ru(L1)Cl3] Cl using
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RuCl3 3H20 (0.393 g, 1.5 mmol) and L2 Cl2 (0.650 g,
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0.75 mmol). (Yield, 0.693 g, 87%).
Anal. Found: C, 59.79; H, 4.57; N, 9.14; Cl, 16.88; Ru, 9.43.
Calcd for C53H49Cl5N7Ru (%): C, 59.92; H, 4.65; N, 9.23; Cl,
16.69; Ru, 9.51.
1H NMR (DMSO-d6), δ ppm: 9.45 (s, 2H), 9.36 (s, 2H), 9.10
(d, 4H, 3J = 8.7 Hz), 9.08 (d, 2H, 3J = 6.5 Hz), 8.81 (m, 2H),
8.49 (d, 2H, 3J = 8.1 Hz), 8.36 (d, 2H, 3J = 8.3 Hz), 8.21-8.00
(m, 6H), 7.90 (d, 2H, 3J = 6.5 Hz), 7.60 (dd, 2H, 3J = 8.3 Hz),
7.58 (d, 2H, 3J = 8.3 Hz), 7.53 (d, 2H, 3J = 8.3 Hz), 7.30-7.20
(m, 4H), 7.01 (d, 2H, 3J = 8.9 Hz), 6.91 (d, 1H, 3J = 8.7 Hz),
6.80 (d, 1H, 3J = 8.7 Hz), 5.84 (s, 2H, -CH2-py+), 3.13 (s, 6H,
N-CH3), 3.03 (s, 6H, N-CH3). UV-visible (CH3CN) [λmax
(nm); (εmax) (M-1 cm-1)]: 500 (45020), 308 (57750), 283 (51240).
ESI Mass Spectrum (m/z) (positive mode): 333.6 ([M]3+/3),
572.9 ([M+PF6]2+/2). Anal. Found: C, 50.28; H, 3.73; N,
8.91; Ru, 7.12; P, 6.64; F, 23.97. Calcd for C60H52N9RuP3F18
(%): C, 50.22; H, 3.65; N, 8.78; Ru, 7.04; P, 6.48; F, 23.83.
[Zn(L1)Cl3]. ZnCl2 2H20 (0.517 g, 3 mmol) was dissolved in
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ethanol (20 mL). A solution of L1 Br (0.941 g, 1.5 mmol) in
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ethanol (40 mL) was added to the previous solution, and the
resulting mixture was stirred at reflux for 3 h. The mixture was
filtrated while hot, and the precipitate was vigorously washed
with ethanol (3 ꢀ 20 mL) and diethyl ether (2 ꢀ 20 mL). The
product was dried under vacuum over P2O5 (Yield, 1 g, 93%).
Anal. Found: C, 61.57; H, 4.41; N, 9.63; Zn, 9.02; Cl, 14.93.
Calcd for C37H32N5ZnCl3 (%): C, 61.86; H, 4.49; N, 9.75; Zn,
9.10; Cl, 14.80.
[Ru(L1)2] (PF6)4 - (Ru-1). [Ru(L1)Cl3] Cl (0.079 g, 0.1 mmol)
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[Zn(tpy-NMe2)(L1)] (PF6)3 - (Zn-10). [Zn(L1)Cl3] (0.072 g,
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and L1 Br (0.063 g, 0.1 mmol) were refluxed overnight in a
0.1 mmol) and tpy-NMe2 (0.036 g, 0.1 mmol) were refluxed for
one night in a mixture of EtOH/H2O (50/20 mL). The resulting
solution was cooled to room temperature and concentrated
under reduced pressure to about 25 mL. Then, water (80 mL)
was added, followed by an aqueous solution of NH4PF6
(200 mg, 5 mL). The resulting orange-red solid was filtered,
washed successively with ethanol (3 ꢀ 10 mL) and diethyl ether
(3 ꢀ 10 mL). As for Ru-10, the product was purified by addition
of diethyl ether to a solution of Zn-10 in acetonitrile (Yield,
110 mg, 78%).
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mixture of EtOH/H2O/DMF (45/15/3 mL). The mixture was
cooled to room temperature, and an aqueous solution of
NH4PF6 (0.200 g, 5 mL) was added. The resulting mixture
was concentrated under vacuum to about 25 mL, and 80 mL
of water were added. The dark-red solid was filtered and washed
successively with water (3 ꢀ 10 mL), ethanol (3 ꢀ 10 mL), and
diethyl ether (3 ꢀ 10 mL). Then, the crude product was purified
by flash column chromatography (Rf = 0.4, Al2O3, sat. aq.
KNO3/CH3CN: 5/95). The eluted solution was concentrated
under reduced pressure. The purified complex (which is con-
stituted of a mixture of hexafluorophosphate and potassium
1H NMR (DMSO-d6), δ ppm: 9.36 (s, 2H), 9.25 (s, 2H),
9.13 (d, 2H, 3J = 10 Hz), 9.11 (d, 3J = 10 Hz, 2H), 9.00 (d, 2H, 3