Journal of the Iranian Chemical Society
3
microscopy (TEM) was performed using Zeiss Libra (120,
Carl Zeiss AG, Oberkochen, Germany) system. The ther-
mal stability of specimens was tested using (PerkinElmer
TGA7 1991, Waltham, MA, USA) thermogravimetric ana-
lyzer from ambient temperature to 900 °C at a heating rate
of 20 °C/min under nitrogen gas. Cyclic voltammograms
were carried out by a SAMA Research Analyzer M-500. A
conventional three-electrode Ag wire and a glassy carbon
were used as a reference and a working electrode, respec-
tively. The working electrode (Metrohm 6.1204.110, with
2Ar-H, J = 7.5), 7.297–7.343 (m 4Ar-H), 8.255–8.260
5
13
(d, 2HC=N, J = 2.5). C NMR (DMSO-d6, δ, ppm):
4
3
7.51–7.57 (d, J = 3, CH ), 14.68–14.88 (d, J = 10, CH ),
3
2
58.79 (CH bridge), 115.62, 119.52, 122.49, 134.68, 135.31
2
3
1
and 164.74 (C-Ar), 167.98 (CH=N). P NMR (DMSO-d6,
δ, ppm): 40.73.
[Co(5-MeOSalen)(PEt )(H O)[ClO ; FT-IR(KBr
3
2
4
−
1
cm ) ν
(N)(1629), (C=C)(1471), (C–O)(1294), (C–H)
max
−
(2834–3045), (ClO )(1092); UV–Vis (λ ) (nm)(Ethanol),
4
max
(654)(500), (428)(13,400), (256)(48,400), (210)(28,900);
1
2.0 ± 0.1 mm diameter) was polished and cleaned with 1 μm
H NMR (DMSO-d6, δ, ppm): 0.920–0.969 (m, 9H, CH ),
3
alumina prior to each scan. Tetrabutylammonium perchlo-
rate (TBAP) was used at the supporting electrolyte. The
solution was deoxygenated by Ar for 5 min. All electro-
1.446–1.516 (m, 6H, CH ), 3.949 (s, 4H, CH ), 6.862–6.866
2
2
4
(d, 2Ar-H, J = 2.5), 6.997–7.053 (m, 2Ar-H), 7.297–7.343
5
13
(m, 4Ar-H), 8.181–8.210 (d, 2HC=N, J = 2.5).
C
+
/0
4
chemical potentials were calibrated versus an internal Fc
NMR (DMSO-d6, δ, ppm): 7.56–7.61 (d, J = 2.5, CH ),
3
0
3
(
E = 0.45 V vs. SCE) couple under the same condition [27].
14.63–14.83 (d, J = 10, CH ), 55.90 (O–CH ), 58.76 (CH
2
3
2
bridge), 114.95, 118.22, 123.18, 124.57, 149.39, and 159.91
3
1
Synthesis of the Schiꢀ base ligands
(C–Ar), 167.47 (CH=N). P NMR (DMSO-d6, δ, ppm):
9.76.
3
−
1
The Schiꢀ base ligands were synthesized by condensation of
[Co(5-BrSalen)(PEt )(H O) [ClO ; FT-IR(KBr cm )
3 2 4
1
,2-ethylenediamine and benzaldehyde derivatives (1:2 mol
νmax (C=N) (1631), (C=C) (1456), (C–O) (1302), (C–H)
−
ratio) in methanol [28].
(2870–3070),(ClO ) (1088); UV–Vis (λ ) (nm) (Etha-
4
max
−
1
X Salen; FT-IR (KBr cm ) ν
X = H (C=N)(1635),
max
nol), (630) (500), (412)(2700), (320)(4700), (256)(67,900),
2
1
(
(
(
(
C=C)(1577), (C–O)(1283); X = MeO (C=N)(1617), (C–C)
(205)(27,200); H NMR (DMSO-d6, δ, ppm): 0.913–0.992
1492), (C–O)(1265); X = Br (C=N)(1634), (C=C)(1473),
(m, 9H, CH ), 1.473–1.567 (m, 6H, CH ), 3.946 (s, 4H,
3
2
3
C–O)(1276); X = NO (C=N)(1612), (C=C)(1540), (C–O)
CH ), 7.004–7.022 (d, 2Ar-H, J = 10), 7.397–7.420 (dd,
2
3 4 4
2
1215), (NO )(1324).
2Ar-H, J = 10, J = 2.5), 7.550–7.555 (d 2Ar-H, J = 2.5),
5
2
13
UV–Vis, λ
(nm) (Ethanol): X = H 318(11,400),
8.233–8.239 (d, 2HC=N, J = 2.5). C NMR (DMSO-d6, δ,
max
4
3
2
2
2
2
60(31,100), 216 (57,600); X = MeO 346(17,700),
ppm): 7.56–7.61 (d, J = 2.5, CH ), 14.91–15.11 (d, J = 10,
3
58(29,700), 230(47,900); X = Br 322(7700), 247(29,500),
CH ), 59.06 (CH bridge), 105.71, 121.17, 124.68, 135.97,
2
2
3
1
24(44,700); X = NO 374(24,000), 250(25,100),
137.61 and 163.73 (C–Ar), 167.53 (CH=N). P NMR
2
36(27,000).
(DMSO-d6, δ, ppm): 42.71.
[
Co(5-NO Salen)(PEt )(H O)[ClO ;FT-IR(KBr
2 3 2 4
−
Synthesis of the Schiꢀ base metal complexes
cm ) ν
(C=C) (1466), (C=N) (1633), (C–H)
max
(
2885–3110),(ClO ) (1105),(N–O) (1314); UV–Vis
4
1
1
.0 mmol of cobalt(II)acetatetetrahydrate (0.249 g) and
.0 mmol of triethylphosphine ((0.144 ml) were added to an
(λ ) (nm)(Ethanol), (635)(900) (366)(31,600), (252)
max
1
(43,900), (212)(26,500); H NMR (DMSO-d6, δ, ppm):
ethanolic solution of X Salen (1.0 mmol, X = H: 0.268 g,
0.934–0.996(m, 9H, CH ), 1.554–1.594 (m, 6H, CH ), 4.014
2
3
2
3
NO 0.358 g, MeO 0.328 g and Br 0.426 g) and reꢂuxed
(s, 4H, CH ), 7.170–7.188 (d, 2Ar-H, J = 9), 8.146–8.170
2
2
1
3
under inert atmosphere for 2 h. The solution was subjected
by blowing air for 2 h to oxidize the Co(II) complex, and
then, it was ꢁltered. Furthermore, 1.0 mmol of sodium per-
chlorate (0.140 g) was added to the ꢁltrate, and the resulting
crystal was appeared after 5 days. The suitable crystals of
(m, 2Ar-H), 8.494–8.506 (m 2Ar-H, and 2HC=N).
C
3
NMR (DMSO-d6, δ, ppm): 7.60–7.66 (d, J = 3, CH ),
3
3
15.29–15.49 (d, J = 10, CH ), 59.32 (CH bridge), 119.00,
2
2
123.05, 129.58, 132.42, 136.79 and 169.01 (C–Ar), 170.24
3
1
(CH=N). P NMR (DMSO-d6, δ, ppm): 46.60.
[
Co(5-BrSalen)(PEt )(H O) [ClO for X-ray were obtained
3 2 4
from methanol after 5 days.
−
1
[
max
Co(Salen)(PEt )(H O)[ClO ; FT-IR (KBR cm
)
Synthesis of intercalation compounds
3
2
4
ν
(C=N) (1625), (C=C) (1448), (C=O)(1304), (C–H)
−
(
(
(
2870–3058), (ClO )(1092). UV–Vis (λ ) (nm)(Ethanol)
An appropriate amount of MMT-K10 (0.75 g) was dispersed
to methanolic solution containing [Co(Salen)(PEt )(H O)
4
max
626)(840), (401)(7400), (320)(9200), (256)(66,000), (210)
3
2
1
28,100); H NMR (DMSO-d6, δ, ppm): 0.905–0.967 (m,
[ClO , [Co(5-NO Salen)(PEt )(H O)[and [Co(Salen)(PBu )
4 2 3 2 3
9
H, CH ), 1.458–1.528 (m, 6H, CH ), 3.949 (s, 4H, CH
(H O)[ClO (about 0.08 g) complexes. The reaction suspen-
2 4
3
2
2
3
bridge), 6.610–6.639 (t, 2Ar-H, J = 7.5), 7.062–7.079 (d,
sion was further reꢂuxed for 24 h. The green precipitates
1
3