Inorganic Chemistry
Article
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Hz, 2H, −CH2); 3.82 (s, 3H, N−CH3); 2.85 (t, J = 7.3 Hz, 2H,
−CH2) ppm; 13C NMR (100 MHz, [D6]DMSO): δ = 136.9, 135.6,
134.2, 125.5, 123.9, 122.8, 117.6, 115.1, 115.0, 50.8, 36.2, 35.6 ppm.
ESI MS: m/z = 217.1 [M-Br−]+. Anal. Calcd for C12H17BrN4.H2O
(315.21): C 45.72, H 6.08, N 17.77. Found: C 45.66, H 5.47, N
17.33%.
were added. A red hygroscopic solid was obtained. Yield: 65%. H
NMR (400 MHz, [D6]DMSO): δ = 9.24 (s, 1H, -NCH-N); 9.05 (d,
J = 7.2 Hz, 2H, -NCH); 8.89 (d, J = 7.2 Hz, 2H, -NCH-N); 8.31
(s, 1H, imid-H); 8.17 (d, J = 8.8 Hz, 1H, imid-H); 7.83 (s, 1H, Ar−
H); 7.74 (d, J = 7 Hz, 3H, Ar−H); 7.69 (s, 2H, Ar−H); 7.41 (s, 1H,
Ar−H); 7.39 (s, 2H, Ar−H); 7.25−7.21 (m, 2H, imid-H); 6.87 (dd, J
= 4 Hz, J = 8.8 Hz, 2H, imid-H); 5.46 (s, 2H, −CH2); 4.40 (dd, J = 6.9
Hz, J = 12.6 Hz, 4H, −CH2); 3.88 (s, 3H, N−CH3); 3.83 (d, J = 3.6
Hz, 6H, N−CH3)); 3.05 (dd, J = 6.9 Hz, J = 12.6 Hz, 4H, −CH2)
ppm; ESI MS: m/z = 939.0 [M-Br−]+, 893.0 [M-I−]+. Anal. Calcd for
C37H39BrI2N8NiO2.6H2O (1128.26): C 39.39, H 4.55, N 9.93. Found:
C 39.52, H 4.46, N 10.20%. λ (nm)/ε (M−1·cm−1), HEPES-buffered
saline (pH 7.4): 370 (18800).
Complex 6. This preparation closely followed the synthesis of
complex 1, starting from IIc (100 mg, 0.27 mmol) in MeOH (4 mL),
Ni(OAc)2·4H2O (34 mg, 0.135 mmol) in MeOH (2 mL), IIIc (38
mg, 0.135 mmol) in MeOH (2 mL), and triethylamine (40 μL, 0.29
mmol) were added. A brown hygroscopic solid was obtained. Yield:
Complex 1. To a solution of 3-(3-formyl-4-hydroxybenzyl)-1-
methyl-1H-imidazol-3-ium41 chloride (100 mg, 0.4 mmol) dissolved in
MeOH (4 mL) was added Ni(OAc)2·4H2O (50 mg, 0.2 mmol) in
MeOH (2 mL) and o-phenylenediamine (21.5 mg, 0.2 mmol) in
MeOH (2 mL). Triethylamine (60 μL, 0.43 mmol) was added to the
resulting red solution. The reaction mixture was refluxed for 1 d. After
it cooled at r.t., the mixture was evaporated and taken up in diethyl
ether. The precipitate was then filtered to give a red hygroscopic
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powder. Yield: 47%. H NMR (400 MHz, [D6]DMSO): δ = 9.34 (s,
2H, -NCH); 9.15 (s, 2H, -NCH-N); 8.18−8.16 (m, 2H, Ar−H);
7.78 (d, J = 9.5 Hz, 4H, imid-H); 7.73 (s, 2H, Ar−H); 7.40−7.34 (m,
4H, Ar−H); 6.90 (d, J = 8.8 Hz, 2H, Ar−H); 5.35 (s, 4H, −CH2);
3.88 (s, 6H, N−CH3) ppm; ESI MS: m/z = 281.1 [M-2Cl−]2+. Anal.
Calcd for C30H28Cl2N6NiO2.8H2O (778.30): C 46.30, H 5.70, N
10.80. Found: C 46.60, H 5.93, N 10.52%. λ (nm)/ε (M−1·cm−1),
HEPES-buffered saline (pH 7.4): 365 (20500).
Complex 2. This preparation closely followed the synthesis of
complex 1, starting from Ic (100 mg, 0.28 mmol) in MeOH (4 mL),
Ni(OAc)2·4H2O (35 mg, 0.14 mmol) in MeOH (2 mL), o-
phenylenediamine (15 mg, 0.14 mmol) in MeOH (2 mL), and
triethylamine (43 μL, 0.31 mmol) were added. A red hygroscopic solid
was obtained. Yield: 42%. 1H NMR (400 MHz, [D6]DMSO): δ = 9.01
(s, 2H, -NCH); 8.80 (s, 2H, -NCH-N); 8.10−8.11 (m, 2H, Ar−
H); 7.71 (s, 2H, imid-H); 7.67 (s, 2H, imid-H); 7.35 (s, 4H, Ar−H);
7.18 (d, J = 8.4 Hz, 2H, Ar−H); 6.84 (d, J = 8.4 Hz, 2H, Ar−H);
4.40−4.36 (m, 4H, −CH2); 3.82 (s, 6H, N−CH3); 3.05−3.01 (m, 4H,
−CH2) ppm; ESI MS: m/z = 295.1 [M-2I−]2+. Anal. Calcd for
C32H32I2N6NiO2.H2O (863.15): C 44.53, H 3.97, N 9.74. Found: C
44.71, H 3.87, N 9.61%. λ (nm)/ε (M−1·cm−1), HEPES-buffered saline
(pH 7.4): 370 (24550).
Complex 3. This preparation closely followed the synthesis of
complex 1, starting from IIc (100 mg, 0.27 mmol) in MeOH (4 mL),
Ni(OAc)2·4H2O (34 mg, 0.135 mmol) in MeOH (2 mL), o-
phenylenediamine (15 mg, 0.135 mmol) in MeOH (2 mL), and
triethylamine (40 μL, 0.29 mmol) were added. A red hygroscopic solid
was obtained. Yield: 58%. 1H NMR (400 MHz, [D6]DMSO): δ = 9.11
(s, 2H, -NCH); 8.82 (s, 2H, -NCH-N); 8.13−8.11 (m, 2H, Ar−
H); 7.79 (s, 2H, imid-H); 7.71 (s, 2H, imid-H); 7.39−7.34 (m, 4H,
Ar−H); 7.21 (dd, J = 2 Hz, J = 8.8 Hz, 2H, Ar−H); 6.85 (d, J = 8.8
Hz, 2H, Ar−H); 4.22−4.19 (m, 4H, −CH2); 3.85 (s, 6H, N−CH3);
2.12−2.09 (m, 4H, −CH2) ppm; ESI MS: m/z = 309.2 [M-2I−]2+.
Anal. Calcd for C34H36I2N6NiO2.H2O (891.21): C 45.82, H 4.30, N
9.43. Found: C 45.50, H 4.41, N 9.46%. λ (nm)/ε (M−1·cm−1),
HEPES-buffered saline (pH 7.4): 370 (26750).
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53%. H NMR (400 MHz, [D6]DMSO): δ = 9.38 (s, 1H, -NCH-
N); 9.24 (s, 1H, -NCH); 9.18 (s, 1H, -NCH); 9.00 (s, 1H, -N
CH-N); 8.91 (s, 1H, -NCH-N); 8.46 (s, 1H, imid-H); 8.20 (d, J =
8.8 Hz, 1H, imid-H); 7.89 (s, 1H, Ar−H); 7.82 (d, J = 8.8 Hz,2H, Ar−
H); 7.74−7.70 (m, 3H, Ar−H); 7.49 (s, 1H, Ar−H); 7.44 (s, 2H, Ar−
H); 7.24 (d, J = 8.8 Hz, 2H, imid-H); 6.87 (dd, J = 2.9 Hz, J = 8.8 Hz,
2H, imid-H); 5.47 (s, 2H, −CH2); 4.24−4.20 (m, 4H, −CH2); 3.89 (s,
6H, N−CH3); 3.86 (s, 3H, N−CH3); 2.97 (broad, 4H, −CH2); 2.13−
2.09 (m, 4H, −CH2) ppm; ESI MS: m/z = 967.0 [M-Br−]+, 921.0 [M-
I−]+. Anal. Calcd for C39H43BrI2N8NiO2.4H2O (1120.28): C 41.81, H
4.59, N 10.00. Found: C 41.77, H 4.83, N 9.94%. λ (nm)/ε (M−1·
cm−1), HEPES-buffered saline (pH 7.4): 375 (17000).
Complex 7. This preparation closely followed the synthesis of
complex 1, starting from IIc (100 mg, 0.27 mmol) in EtOH (4 mL),
Ni(OAc)2·4H2O (34 mg, 0.135 mmol) in EtOH (2 mL), IVf (40 mg,
0.135 mmol) in EtOH (2 mL), and triethylamine (40 μL, 0.29 mmol)
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were added. A red hygroscopic solid was obtained. Yield: 78%. H
NMR (400 MHz, [D6]DMSO): δ = 9.25 (s, 1H, -NCH-N); 9.19 (s,
2H, -NCH); 8.98 (s, 1H, -NCH-N); 8.83 (s, 1H, -NCH-N);
8.27 (s, 1H, imid-H); 8.07 (d, J = 8.8 Hz, 1H,imid-H); 7.84 (s, 1H,
Ar−H); 7.81 (s, 1H, Ar−H); 7.76 (s, 1H, Ar−H); 7.72 (s, 2H, Ar−H);
7.68 (s, 1H, Ar−H); 7.52 (s, 1H, imid-H); 7.42 (s, 1H, imid-H);
7.24−7.17 (m, 3H, Ar−H); 6.85 (dd, J = 4.2 Hz, J = 8.8 Hz, 2H, imid-
H); 4.64−4.60 (m, 2H, −CH2); 4.24−4.20 (m, 4H, −CH2); 3.87 (d, J
= 6.6 Hz, 6H, N−CH3); 3.84 (s, 3H, N−CH3); 3.24 (broad, 2H,
−CH2); 2.92−2.91 (m, 4H, −CH2); 2.15−2.09 (m, 4H, −CH2) ppm;
ESI MS: m/z = 981.1 [M-Br−]+, 935.1 [M-I−]+. Anal. Calcd for
C40H45BrI2N8NiO2.6H2O (1170.34): C 41.05, H 4.91, N 9.57. Found:
C 40.99, H 5.25, N 9.02%. λ (nm)/ε (M−1·cm−1), HEPES-buffered
saline (pH 7.4): 375 (14 400).
Complex 8. This preparation closely followed the synthesis of
complex 1, starting from 3-(3-formyl-4-hydroxybenzyl)-1-methyl-1H-
imidazol-3-ium chloride (100 mg, 0.4 mmol) in MeOH (4 mL),
Ni(OAc)2.4H2O (50 mg, 0.2 mmol) in MeOH (2 mL), IVf (59 mg,
0.2 mmol) in MeOH (2 mL), and triethylamine (60 μL, 0.43 mmol)
Complex 4. This preparation closely followed the synthesis of
complex 1, starting from 3-(3-formyl-4-hydroxybenzyl)-1-methyl-1H-
imidazol-3-ium chloride (100 mg, 0.4 mmol) in MeOH (4 mL),
Ni(OAc)2·4H2O (50 mg, 0.2 mmol) in MeOH (2 mL), IIIc (57 mg,
0.2 mmol) in MeOH (2 mL), and triethylamine (60 μL, 0.43 mmol)
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were added. A brown hygroscopic solid was obtained. Yield: 68%. H
NMR (400 MHz, [D6]DMSO): δ = 9.39 (s, 1H, -NCH-N); 9.31 (s,
2H, -NCH); 9.26 (s, 1H, -NCH-N); 9.18 (s, 1H, -NCH-N);
8.32 (s, 1H, Ar−H); 8.08 (d, J = 8 Hz, 1H, imid-H); 7.79−7.74 (m,
6H, Ar−H); 7.69 (s, 2H, Ar−H); 7.39 (s, 2H, imid-H); 7.21 (d, J = 8
Hz, 1H, imid-H); 6.92 (d, J = 8 Hz, 2H, imid-H); 5.35 (d, J = 10 Hz,
4H, −CH2); 4.65−4.62 (m, 2H, −CH2); 4.04−4.03 (m, 2H, −CH2);
3.88 (d, J = 10 Hz, 6H, N−CH3); 3.84 (s, 3H, N−CH3) ppm; ESI MS:
m/z = 743.2 [M-Br−]+. Anal. Calcd for C36H37BrCl2N8NiO2.8H2O
(967.36): C 44.70, H 5.52, N 11.58. Found: C 44.57, H 5.81, N
11.31%. λ (nm)/ε (M−1·cm−1), HEPES-buffered saline (pH 7.4): 367
(19750).
Complex 9. This preparation closely followed the synthesis of
complex 1, salicylaldehyde (100 mg, 0.82 mmol) in MeOH (4 mL),
Ni(OAc)2.4H2O (102 mg, 0.41 mmol) in MeOH (2 mL), IIIc (123
mg, 0.41 mmol) in MeOH (2 mL), and triethylamine (126 μL, 0.90
mmol) were added. A brown hygroscopic solid was obtained. Yield:
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were added. A brown hygroscopic solid was obtained. Yield: 68%. H
NMR (400 MHz, [D6]DMSO): δ = 9.58 (s, 1H, -NCH-N); 9.28 (d,
J = 10 Hz, 2H, -NCH); 8.56 (s, 1H, -NCH-N); 8.21 (d, J = 8.8
Hz, 1H, imid-H); 7.94 (s, 2H, -NCH-N); 7.77 (s, 4H, Ar−H); 7.73
(s, 5H, Ar−H); 7.47 (d, J = 8.8 Hz, 1H, imid-H); 7.41 (d, J = 8.8 Hz,
2H, imid-H); 6.91 (d, J = 8.8 Hz, 2H, imid-H); 5.48 (s, 2H, −CH2);
5.34 (d, J = 4.2 Hz, 4H, −CH2); 3.88 (s, 6H, N−CH3); 3.86 (s, 3H,
N−CH3) ppm; ESI MS: m/z = 773.1 [M-Cl−]+, 729.2 [M-Br−]+. Anal.
Calcd for C35H35BrCl2N8NiO2.8H2O (953.33): C 44.09, H 5.39, N
11.75. Found: C 44.01, H 6.17, N 11.6%. λ (nm)/ε (M−1·cm−1),
HEPES-buffered saline (pH 7.4): 370 (15 560).
Complex 5. This preparation closely followed the synthesis of
complex 1, starting from Ic (100 mg, 0.28 mmol) in MeOH (4 mL),
Ni(OAc)2.·H2O (35 mg, 0.14 mmol) in MeOH (2 mL), IIIc (40 mg,
0.14 mmol) in MeOH (2 mL), and triethylamine (43 μL, 0.31 mmol)
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dx.doi.org/10.1021/ic502063r | Inorg. Chem. XXXX, XXX, XXX−XXX