Molecules 2017, 22, 1860
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1
H-NMR (400 MHz, DMSO-d ):
δ
9.48 (s, 2H), 8.75 (t, 1H, J 1.7), 8.42 (dd, 4H, J 8.1 and 1.8 Hz), and
6
.85 (t, 1H, J 7.9 Hz). 13C { H}:
1
δ
164.36 (C5, C5’), 154.22 (C7, C7’), 147.59 (C2, C2’), 136.86 (C6, C6’),
7
1
3
34.38 (C4), 131.25 (C3, C3’), and 129.32 (C1) Anal. calcd. for C H N O : C, 53.73; H, 3.01; and N,
12 8 6 2
1.33; found: C, 53.57; H, 3.04; and N, 29.65%. MS (FTMS + IT) m/z, calcd. for [M + Na] : 291.062;
+
found: 291.062.
3
.3. Synthesis of Catena-Poly[chlorocobalt-di-µ-chloro-cobalt-µ-[1,3-Phenylenebis(1,2,3-triazole-1-yl)-
methanone-O:N,O’:N’]] (2)
A solution of (0.38 mmol; 101 mg) in a 1:1mixture of acetone:ethanol (4 mL) was added to
1
a solution of cobalt(II) chloride (0.38 mmol; 49.5 mg) in acetone (5 mL). The reaction mixture was
stirred at room temperature (rt) for 1 h. The resulting light blue solid was filtered off, washed
◦
◦
with acetone and ethanol, and dried at 80 C for 12 h. Yield: 97.0 mg (65%). M.p.: >400 C
(
−
1
decomposition); IR (KBr) ν/cm : 3126, 3017, 2912, 2827, 2361, 1700, 1521, 1422, 1312, 1064, 884,
6
18, and 419. Anal. calcd. for C H Cl Co N O : C, 27.28; H, 1.52; and N, 15.91; found: C, 27.08; H,
12
8
4
2
6
2
1
.51; and N, 15.20%.
3
.4. Synthesis of Catena-Poly[chlorocopper-di-µ-chloro-copper-µ-[1,3-Phenylenebis(1,2,3-triazole-1-yl)-
methanone-O:N,O’:N’]] (3)
A solution of
1 (0.74 mmol; 198.0 mg) in acetone (3 mL) was added to a solution of copper(II)
chloride (0.75 mmol; 100.7 mg) in acetone (3 mL). The reaction mixture was stirred for 5 h at rt.
The resulting blue solid was filtered off; washed with acetone, dichloromethane and diethyl ether; and
◦
◦
−1
:
dried at 80 C for 12 h. Yield: 146.0 mg (49%). M.p.: 340 C (decomposition). IR (KBr)
448, 3135, 3024, 2926, 1708, 1519, 1427, 1373, 1215, 1079, 955, 876, 717, and 620. Anal. calcd.
for C H Cl Cu N O : C, 26.81; H, 1.49; and N, 15.64; found: C, 26.61; H, 1.50; and N, 15.67%.
ν
/cm
3
12
8
4
2
6
2
3
.5. Synthesis of Catena-Poly[chlorozinc-di-
µ-chloro-zinc-µ-[1,3-Phenylenebis(1,2,3-triazole-1-yl)-methanone-
O:N,O’:N’]] (4)
A solution of
1 (0.188 mmol; 50.5 mg) in acetone (2 mL) was added to a solution of zinc(II)
chloride (0.19 mmol; 26.5 mg) in acetone (1 mL). The reaction mixture was stirred for 1 h at rt.
The resulting white solid was filtered off, washed with acetone and ethanol, and dried under a vacuum.
◦
−1
Yield: 31.0 mg (40%). M.p.: >400 C (decomposition); IR (KBr)
H NMR (400 MHz, DMSO-d6):
ν
/cm : 3118, 1691, 1418, 1223, and 420.
1
δ 9.49 (s, 2H, 2,2’), 8.76 (t, 1H, J 1.7 Hz), 8.42 (dd, 4H, J 8.1 and 1.8 Hz),
and 7.85 (t, 1H, J 7.9 Hz). Anal. calcd. for C H Cl ZnN O : C, 35.60; H, 1.98; and N, 20.76; found: C,
12
8
2
6
2
3
5.15; H, 1.88; and N, 20.72%.
3
.6. Synthesis of Catena-Poly[chloronickel-di-µ-chloro-nickel-µ-[1,3-Phenylenebis(1,2,3-triazole-1-yl)-
methanone-O:N,O’:N’]] (5)
To a Schlenk tube equipped with a reflux condenser was added nickel(II) chloride (0.39 mmol;
49.8 mg) in methanol (12 mL) and the mixture was refluxed for 30 min. Then, 1 (0.60 mmol; 160.2
mg) was added, and the mixture was refluxed for an additional 72 h. The resulting light violet solid
◦
was filtered off, washed with tetrahydrofuran and diethyl ether, and dried at 80 C for 12 h. Yield:
9
◦ −1
4.0 mg (63%). M.p.: >400 C (decomposition). IR (KBr) ν/cm : 3134, 2907, 1630, 1524, 1427, 1310,