Synthesis and spectral studies of macrocyclic Cu(II), Ni(II) and Co(II) complexes by template reaction of 1,4-bis(3-aminopropoxy)butane with metal(II) nitrate and salicylaldehyde derivatives

Article abstract of DOI:10.1016/j.molstruc.2008.03.016

Six new macrocyclic complexes were synthesized by template reaction of salicylaldehyde derivatives with 1,4-bis(3-aminopropoxy)butane and metal(II) nitrate. The metal to ligand ratio of the complexes was found to be 1:1. The Cu(II) complexes are proposed

Full text of DOI:10.1016/j.molstruc.2008.03.016

Journal of Molecular Structure 891 (2008) 157–166
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstruc
Synthesis and spectral studies of macrocyclic Cu(II), Ni(II) and Co(II) complexes
by template reaction of 1,4-bis(3-aminopropoxy)butane with metal(II) nitrate
and salicylaldehyde derivatives
Salih Ilhan a,*, Hamdi Temel b
a
Department of Chemistry, Faculty of Art and Sciences, Siirt University, Siirt, Turkey
Department of Chemistry, Faculty of Education, Dicle University, Diyarbakir, Turkey
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Six new macrocyclic complexes were synthesized by template reaction of salicylaldehyde derivatives
with 1,4-bis(3-aminopropoxy)butane and metal(II) nitrate. The metal to ligand ratio of the complexes
was found to be 1:1. The Cu(II) complexes are proposed to be square planar and the Ni(II) and Co(II) com-
Received 20 September 2007
Received in revised form 11 March 2008
Accepted 12 March 2008
plexes are proposed to be tetrahedral geometry. Macrocyclic complexes are 1:2 electrolytes as shown by
Available online 21 March 2008
À3
their molar conductivities (K
M
) in DMF (dimethylformamide) of 10 M solution. The structure of metal
complexes is proposed from elemental analysis, FTIR, UV–vis, magnetic susceptibility measurements,
molar conductivity measurements and mass spectra.
Keywords:
Macrocyclic Schiff base
Macrocyclic Schiff base complex
Salicylaldehyde derivatives
Ó 2008 Elsevier B.V. All rights reserved.
1
1
,2-Bis(2-formylphenyl)ethane or
,3-bis(2-formylphenyl)propane
1
. Introduction
The preparation of macrocyclic polyamine ligands bearing
19] or transmetallation reactions [20–23] which are used when
the transition metal cations are ineffective as templates. The tox-
icity of these metals on a biological system is connected with
the displacing the essential metal ions in biomolecules, blocking
the functional groups and inhibiting or enhancing their enzy-
matic activities. The synthesis of potential chelating agents for
effective sequestering and removing toxic metal ions from the
human body is a field of growing interest [24]. In the present
work, we have synthesized six macrocyclic Schiff base complexes
by template effect by reaction of metal(II) nitrate with 1,4-bis(3-
aminopropoxy)butane and salicylaldehyde derivatives. Spectral,
magnetic properties of the new compounds were studied in
detail.
functional pendant donor groups and their subsequent ligation
to various metal ions has been an active area of research in re-
cent years [1–3] Macrocyclic ligands containing a heteroatom are
important complexing agents for cations, anions and molecules
[
4,5]. The stability of macrocyclic metal complexes depends upon
a number of factors, including the number and type of donor
atoms present in the ligand and their relative positions within
the macrocyclic skeleton, as well as the number and size of
the chelate rings formed on complexation. For transition metal
ions, features such as the nature and magnitude of crystal-field
effects play also an important role [6]. Synthetic macrocycles
are a growing class of compounds with varying chemistry a wide
range of different molecular topologies and sets of donor atoms
2
. Experimental
[
7–13]. The chemical properties of macrocyclic complexes can be
2
.1. Physical measurements
tuned to force metal ions to adopt unusual coordination geome-
try. Transition metal macrocyclic complexes have received much
attention as an active part of metalloenzymes [14] as biomimic
model compounds [15] due to their resemblance with natural
proteins like hemerythrin and enzymes. Synthesis of these Schiff
base complexes is achieved through the template reaction [16–
Elemental analysis was carried out on a LECO CHNS model 932
elemental analyzer. IR spectra were recorded on a PERKIN ELMER
SPECTRUM RX1 FTIR spectrophotometer on KBr pellets in the wave
number range of 4000–400 cm . Electronic spectral studies were
conducted on a SHIMADZU model 160 UV–Visible spectrophotom-
eter in the wavelength 200–900 nm. Molar conductivity was mea-
sured with a WTW LF model 330 conductivity meters, using
prepared solution of the complexes in DMF solvent. Magnetic
À1
*
Corresponding author.
E-mail address: salihilhan@dicle.edu.tr (S. Ilhan).
0
022-2860/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2008.03.016

1
58
S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
O
O
O
COH
OH
10 hour at 150-155
hour
º
C
2
+
K CO
+
Br
Br
2
3
+
2KBr + H O + CO2
2
5
at room temperature
O
O
O
COH
OH
10 hour at 150-155
hour
º
C
2
+
K CO
+ Br
Br
2
3
+
2KBr + H O + CO2
2
5
at room temperature
O
O
Fig. 1. Synthesis of 1,2-bis(2-formylphenyl)ethane or 1,3-bis(2-formylphenyl)propane.
Table 1
Physical characterization, analytical, molar conductance and mass data of the complexes
Compound
Yield
(calcd.)
k
M
(X1 cm2 mol-1
)
F.W.
MS/EI
Assigment
leff (BM)
Gram (%)
0.23
Found %C
%H
%N
1
1
]+
)]+
+H]+
+H]+
+H]+
)+H]+
[
[
[
[
[
[
NiL ][NO
3
]
2
Á2H
Á3H
Á2H
Á2H
Á4H
Á3H
2
O
(47.49)
47.67
(46.15)
46.34
(47.06)
47.14
(48.36)
48.44
(45.83)
46.94
(47.09)
46.94
(5.78)
6.04
(5.92)
6.18
(5.73)
6.02
(5.97)
6.12
(6.22)
6.17
(6.10)
5.96
(8.52)
8.29
(8.28)
8.32
(8.45)
8.34
(8.36)
8.55
(7.92)
7.85
(8.14)
8.26
167
179
184
191
171
186
657
675
663
671
709
694
621
559
627
636
636
579
[[NiL ][NO
3
]
2
2.81
3.96
2.02
2.64
3.78
2.17
(
(
(
(
(
(
17.4)
0.29
21.4)
0.31
23.3)
0.19
14.5)
0.30
1
1
CoL ][NO
3
]
2
2
O
[[CoL ](NO
3
1
1
CuL ][NO
3
]
2
2
O
[[CuL ](NO
3
)
2
2
2
NiL ][NO
]
3 2
2
O
[[NiL ](NO
3
)
2
2
2
CoL ][NO
3
]
2
2
O
[[CoL ](NO
3
)
2
21.2)
0.39
28.0)
2
2
CuL ][NO
3
]
2
2
O
[CuL ](NO
3
1
Susceptibilities were determined on a Sherwood Scientific Mag-
2.2.1. Characterization of [NiL ](NO
3
)
2
Á2H
2
O
netic Susceptibility Balance (Model MK1) at room temperature
Yield: 0.23 g (17.4%). Anal. Calcd. for NiC26
47.49, H, 5.78, N, 8.52. Found: C, 47.67, H, 6.04, N, 8.29. Selected
IR data (KBr, m cm ): 3368 m(H
m(Alph.-CH), 1634 m(C@N), 1452, 1450 m(ArAC@C), 1384, 1109,
H
34
N
4
O
10.2H
2
O:ÁC,
o
(
20 C) using Hg[Co(SCN)
4
] as a calibrant; diamagnetic corrections
À1
were calculated from Pascal’s constants [25]. Electrospray ioniza-
tion mass spectrometric analysis (ESI-MS) was obtained on the
AGILENT 1100 MSD spectrometer.
2
O) 3135 m(ArACH), 2967, 2881
À
661 m(NO
3
), 1278, 1242 m(ArAO), 1146, 1041 m(RAO), 752
m(Substituted
benzene),
528
m(NiAO)
475
m(NiAN).
À1
2
À1
2.2. Materials
K
M
= 167 X cm mol
(in DMF). UV–vis (kmax, nm) in DMF:
2
+
2
42, 265, 326, 568. Mass spectrum (m/z): 621 [[NiL ](NO
3 2
) +H] ,
The salicylaldehyde derivatives used in the synthesis were pre-
leff = 2.81 B.M.
pared from salicylaldehyde, 1,2-dibromoethane or 1,3-dibromo-
propane and K CO as shown in Fig. 1 and according to the
literature method [26,27]. All the chemicals and solvents were of
analytical grade and used as received.
1
2
3
2.2.2. Characterization of [CoL ](NO
3
)
2
Á3H
2
O
Yield: 0.29 g (21.4%). Anal. Calcd. for CoC26
46.15, H, 5.92, N, 8.28. Found: C, 46.34, H, 6.18, N, 8.32. Selected IR
data (KBr, m cm ): 3361 m(H
H
34
N
4
O10Á3H
2
O: C,
À1
To a stirred solution of salicylaldehyde derivatives (2 mmol)
2
O), 3076 m(ArACH), 2933, 2881
and M(NO
wise 1,4-bis(3-aminopropoxy)butane (2 mmol) in methanol
40 mL). After the addition was completed, the stirring was contin-
ued for 2 h. Then precipitate was filtered and washed with metha-
nol, then dried in air (M = Cu; n = 3 or M = Co, Ni; n = 6).
3
)
2
ÁnH
2
O (2 mmol) in methanol (60 mL) was added drop-
m(Alph.-CH), 1635 m(C@N), 1491, 1456 m(ArAC@C), 1384, 1161, 654
À
m(NO
3
), 1292, 1247m(ArAO), 1162, 1043, m(RAO), 756m(Substituted
À1
2
À1
(
benzene), 552 m(CoAO) 511 m(CoAN). K = 179 X cm mol (in
DMF). UV–vis (kmax, nm) in DMF: 238, 272, 307, 651. Mass spectrum
1
+
3
(m/z): 559 [[CoL ](NO )] . leff = 3.96 B.M.
Table 2
À1
IR (cm ) spectral data for the complexes
3À
Compound
m(H
2
O)
m(C@N)
Ionic m(NO
)
m(RAO)
m(ArAO)
m(MAO)
m(MAN)
1
[
[
[
[
[
[
NiL ][NO
3
]
2
Á2H
Á3H
Á2H
Á2H
Á4H
Á3H
2
O
2
O
3368 s
3361 s
3342 s
3338 s
3356 s
3349 s
1634 m
1635 m
1634 m
1636 m
1636 m
1635 m
1384 m
1384 m
1384 m
1384 m
1384 m
1384 m
1146, 1041 m
1162, 1043 m
1193, 1091 m
1177, 1052 m
1092, 1038 m
1191, 1046 m
1278, 1242 s
1292, 1247 s
1287, 1243 s
1288, 1246 s
1311, 1239 s
1288, 1246 s
528 w
552 w
517 w
516 w
535 w
515 w
475 w
511 w
476 w
471 w
502 w
473 w
1
CoL ][NO
3
]
2
1
CuL ][NO
3
]
2
2
O
O
2
NiL ][NO
]
3 2
2
2
CoL ][NO
3
]
2
2
O
2
O
2
CuL ][NO
3
]
2
s, strong, m, medium, w, weak.

S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
159
O
N
O
O
+
+
+
O
O
N
O
N
N
Co
(NO3)2
.
3X - 2H
N
Co
(NO3)2
.
3X - H
.
O
N
Co
(NO ) 3X
3 2
O
O
O
O
O
m/z: 673, 18.2%
(m/z: 674, 7.4%)
(m/z: 675, 1.8%)
x = H O
x = H O
x = H O
2
2
2
O
O
O
+
+
+
O
O
N
Co
O
N
N
N
(NO3)
N
Co
O
+5H
+4H
O
N
Co
O
O
O
O
m/z: 559, 2.4%
m/z: 462, 2.6%
m/z: 503, 1.6%
O
+
O
+
+
O
N
O
O
N
Co
O
N
N
N
O
N
-H
Co
+
3H
O
O
O
O
O
m/z: 458, 2.6%
m/z: 457, 32.9%
m/z: 441, 5.8%
+
+
+
O
O
O
N
O
O
N
O
N
N
N
N
+
2H
+H
-H
O
O
O
O
O
O
m/z: 439, 100%
m/z: 400, 2.3%
m/z: 440, 5.8%
+
+
O
+
N
N
N
N
N
N
+
4H
-2H
-H
O
O
O
O
O
O
m/z: 285, 3.8%
m/z: 309, 5.4%
m/z: 356, 1.5%
Á3H O.
1
Fig. 2. The fragments observed in the mass spectrum of the [CoL ](NO
)
3 2
2
1
3À
2
.2.3. Characterization of [CuL ](NO
3
)
2
Á2H
2
O
667 m(NO ), 1287, 1243 m(ArAO), 1193, 1091, m(RAO), 757
Yield: 0.31 g (23.3%). Anal. Calcd. for CuC26
7.06, H, 5.73, N, 8.45. Found: C, 47.14, H, 6.02, N, 8.34. Selected
IR data (KBr, m cm ): 3342 m(H
H
34
N
4
O
10.2H
2
O: C,
m(Substituted
benzene),
517
m(CuAO)
476
m(CuAN).
À1
2
À1
4
K = 184 X cm mol (in DMF). UV–vis (kmax, nm) in DMF: 232,
À1
1
+
2
O), 3070 m(ArACH), 2937, 2831
266, 317, 693. Mass spectrum (m/z): 627 [[CuL ](NO
3 2
) +H] .
m(Alph.-CH), 1634 m(C@N), 1490, 1455 m(ArAC@C), 1384, 1156,
leff = 2.02 B.M.

1
60
S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
+
+
+
N
N
N
N
N
N
-2H
-4H
+3H
O
O
O
O
O
O
m/z: 279, 1.6%
m/z: 277, 17.5%
m/z: 284, 6.9%
+
+
+
N
N
+
4H
+
2H
+2H
O
O
O
O
O
O
m/z: 258, 4.5%
m/z: 258, 12.1%
m/z: 229, 76.1%
+
+
+
+
2H
+
H
O
O
+2H
O
O
O
O
m/z: 139, 7.5%
m/z: 228, 12.9%
m/z: 214, 2.1%
+
+
+
+
-5H
+
H
-3H
O
O
O
O
m/z: 121, 1.0%
m/z: 107, 6.3%
m/z: 101, 7.7%
m/z: 103, 13.0%
+
+
+
4H
+
H
O
m/z: 98, 1.9%
m/z: 79, 18.5%
Fig. 2 (continued)
2
2
.2.4. Characterization of [NiL ](NO
3
)
2
Á2H
2
O
DMF). UV–vis (kmax, nm) in DMF: 243, 282, 312, 667. Mass spectrum
10.2H
(m/z): 636 [[NiL ](NO
2
+
Yield: 0.19 g (14.5%). Anal. Calcd. for NiC27
H
36
N
4
O
2
O: C,
3
)
2
+H] . leff = 2.64 B.M.
4
8.36, H, 5.97, N, 8.36. Found: C, 48.44, H, 6.12, N, 8.55. Selected IR
À1
2
data (KBr, m cm ): 3338 m(H
m(Alph.-CH), 1636 m(C@N), 1489, 1454 m(ArAC@C), 1384, 1161, 626
m(NO
2
O), 3054 m(ArACH), 2936, 2858
2.2.5. Characterization of [CoL ](NO
3
)
2
Á4H
2
O
36 4 2
Yield: 0.30 g (21.2%). Anal. Calcd. for CoC27H N O O: C,
10.4H
45.83, H, 6.22, N, 7.92. Found: C, 45.94, H, 6.17, N, 7.85. Selected
IR data (KBr, m cm ): 3356 m(H
À
3
), 1288, 1246m(ArAO), 1177, 1052, m(RAO), 758m(Substituted
À1
2
À1
À1
benzene), 516 m(NiAO) 471 m(NiAN). K = 191 X cm mol (in
2
O), 3125 m(ArACH), 2923, 2862

S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
161
O
N
O
+
O
N
O
+
N
N
(
NO ) +H
3
Cu
(NO ) -H
3
Cu
O
O
O
O
m/z: 579, 3.1%
m/z: 555, 3.1%
O
N
O
O
N
O
N
O
N
O
+
+
+
N
N
+3H
Cu
Cu
+2H
+H
Cu
O
O
O
O
O
O
m/z: 519, 6.2%
m/z: 518, 32.0%
m/z: 517, 100%
O
O
O
+
+
+
N
N
N
N
N
N
-3H
-2H
Cu
-4H
Cu
Cu
O
O
O
O
O
O
m/z: 471, 18.6%
m/z: 472, 6.0%
m/z: 498, 3.3%
O
N
O
O
N
O
O
N
O
+
+
+
N
N
N
+2H
+3H
+
H
O
O
O
O
O
O
m/z: 453, 89.0%
m/z: 454, 27.4%
m/z: 455, 5.7%
O
+
+
+
N
N
N
N
N
N
-H
+3H
+
2H
O
O
O
O
O
O
m/z: 299, 7.2%
2
O.
m/z: 383, 4.4%
m/z: 349, 3.0%
Fig. 3. The fragments observed in the mass spectrum of the [CuL ](NO
2
3
2
) Á3H
À1
2
À1
m(Alph.-CH), 1634 m(C@N), 1490, 1455 m(ArAC@C), 1384, 1163,
K = 171 X cm mol
238, 268, 322, 649. Mass spectrum (m/z): 636 [[CoL ](NO
leff = 3.78 B.M.
(in DMF). UV–vis (kmax, nm) in DMF:
À
2
+
6
54 m(NO
3
), 1311, 1239 m(ArAO), 1092, 1038, m(RAO), 753
benzene), 535 m(CoAO) 502 m(CoAN).
3 2
) +H] .
m(Substituted

1
62
S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
+
+
+
N
N
N
N
N
N
-H
-3H
+
4H
O
O
O
O
O
O
m/z:: 284, 6.9%
m/z:: 279, 1.5%
m/z : 277, 17.5%
+
+
+
N
N
+
H
+3H
+
H
O
O
O
O
O
O
m/z : 258, 4.5%
m/z : 229, 76.1%
m/z : 256, 12.1%
+
+
+
N
+
H
-3H
+3H
O
O
O
O
O
O
m/z :182, 2.1%
m/z : 228, 12.9%
m/z : 162, 3.0%
+
+
+
-4H
-5H
+
4H
O
O
O
O
O
m/z :148, 18.8%
m/z :147, 87.8%
m/z :139, 7.5%
+
+
+
+
N
N
+
4H
+H
-H
+
H
O
m/z :103, 13.0%
m/z :79, 18.5%
m/z :101, 7.7%
m/z :98, 7.7%
Fig. 3 (continued)
2
2
)+H]+.
3
2
.2.6. Characterization of [CuL ](NO
3
)
2
Á3H
2
O
276, 309, 668. Mass spectrum (m/z): 579 [[CuL ](NO
leff = 2.17 B.M.
Yield: 0.39 g (28.0%). Anal. Calcd. for CuC27
7.09, H, 6.10, N, 8.14. Found: C, 46.94, H, 5.96, N, 8.26. Selected
IR data (KBr, m cm ): 3449 m(H
m(Alph.-CH), 1635 m(C@N), 1490, 1456 m(ArAC@C), 1384, 1107,
H
36
N
4
O
10Á3H
2
O: C,
4
À1
2
O), 3066 m(ArACH), 2935, 2872
3
. Results and discussion
À
6
64 m(NO
3
), 1288, 1246 m(ArAO), 1191, 1046, m(RAO), 754
In this work, the reaction between 1,2-bis(2-formylphenyl)eth-
ane or 1,3-bis(2-formylphenyl)propane with metal(II) nitrate and
,4-bis(3-aminopropoxy)butane in methanol, gave [1+1] macrocy-
m(Substituted
benzene),
515
m(CuAO)
473
m(CuAN).
À1
2
À1
K = 186 X cm mol (in DMF). UV–vis (kmax, nm) in DMF: 240,
1

S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
163
1
Fig. 4. The mass spectra of the [CoL ][NO
]
3 2
Á3H
2
O.
2
Fig. 5. The mass spectra of the [CuL ][NO
3 2
] Á3H
2
O.

1
64
S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
O
O
O
Co
O
N
N
N
N
N
R
Cu
.
.
(
NO ) 2H O
R
Cu
(NO ) 3H O
R
.
3
2
2
3
2
2
(NO ) 3H O
3 2 2
N
O
O
1
.
[
CuL ](NO ) 2H O
2
.
1
.
3
2
2
[CuL ](NO ) 3H O
[CoL ](NO ) 3H O
3 2 2
3
2
2
O
O
O
N
N
N
Ni
Ni
Co
.
R
.
R
.
R
(
NO ) 4H O
3
2
2
(NO ) 2H O
3
2
2
(NO ) 2H O
3 2 2
N
N
N
O
O
O
2
.
2
.
1
.
[NiL ](NO ) 2H O
3 2 2
[
CoL ](NO ) 4H O
[NiL ](NO ) 2H O
3
2
2
3
2
2
O
O
R =
O
O
O
O
N
N
N
N
O
O
O
O
L1
L2
Fig. 6. Suggested Structure of the complexes.
À1
clic Schiff base complexes as the product. The macrocyclic
complexes were characterized by elemental analysis, FTIR, UV–vis,
conductivity measurements, magnetic susceptibility and mass and
spectra. The mass spectra of the complexes play an important role
in confirming the monomeric [1+1] (dicarbonyl and diamine) nature
of complexes (Table 1). The crystals were unsuitable for single-crys-
tal X-ray structural determination and are insoluble in most com-
mon solvents as: water, ethanol, ethyl acetate and/or acetonitrile.
(m
1
) and 1040 (m
2
) cm , suggest the presence of bidentate nitrate
À1
groups: a intense band at ca. 1384 cm attributable to ionic ni-
trate, is also present [29–31]. The spectra of all the complexes
are dominated by bands at 2965–2855 cm due to m(Alph.-CH)
groups [30]. Conclusive evidence of the bonding is also shown by
the observation that new bands in the IR spectra of the complexes
À1
À1
appear at 552–515 and 511–471 cm assigned to m(MAO) and
m(MAN) stretching vibrations [31] (Table 2).
3.1. FTIR spectra
3.2. Electronic absorption spectroscopy
The characteristic infrared spectral data are given in the exper-
Electronic absorption spectral data of the complexes in
dimethylformamide (DMF) at room temperature are presented
in experimental section. The electronic spectra of complexes in
DMF show four bands in the visible–ultraviolet region. The
absorption bands below 300 nm are practically identical and
imental section. Infrared spectra of the complexes were recorded
À1
in KBr pellet from 4000 to 400 cm . The broad bands at ca.
À1
3
350 cm in the spectra of all complexes can be attributed to
2
stretching vibrations of water molecule t(H O) [28]. A medium
*
band observed in the IR spectra of the complexes in the 1636–
can be attributed to p ? p transitions in the benzene ring and
azomethine (AC@N) groups [32]. The absorption bands observed
À1
1
634 cm region which is attributed to the t(C@N) stretch, indi-
cating coordination of the azomethine nitrogen to metal [29].
The absorptions of the nitrate ions, at ca. 1460–1452 (m ), 1300
within the 300–330 nm range are most probably due to the tran-
sitions of n ? p of imine groups [33]. The general character of
*
5

S. Ilhan, H. Temel / Journal of Molecular Structure 891 (2008) 157–166
165
1
+
1
+
these spectra is very similar to that of the corresponding com-
plexes of unsymmetrical desubstituted phenoxy groups. This is
probably due to the fact that metal-to-ligand charge transfer
and ligand-to-metal charge transfer transitions have similar en-
ergy differences [34]. The electronic spectra of the Cu(II) com-
plexes show an absorption band at 668–693 nm attributed to
[[CuL ](NO
3
)
2
À2H] ), (565, 8.4%, [[CuL ](NO
3
)+H] ), (564, 12.3%,
1
+
1
+
[[CuL ](NO
3
)] ), (563, 3.1%, [[CuL ](NO
3
)ÀH] ), (503, 15.2%,
1
+
1 +
1 +
[CuL +H] ), (502, 32.8%, [CuL ] ), (489, 40.3%, [CuL À(CH
2
)+H] ),
1
+
1
+
(488, 59.1%, [CuL À(CH
2
)] ), (441, 48.3%, [L +3H] ), (440, 77.5%,
1
+
1
+
1 +
[L +2H] ), (439, 100%, [L +H] ), (438, 9.3%, [L ] ), (424, 10.9%,
1
+
1
+
+
[L À(CH
2
)] ), (408, 5.9%, [L À(OCH
2
)] ), (98, 17.2%, [C
H
6 6
O+4H] ),
2
2
+
the
E
g
? T2g transition, characteristic for square planar geome-
(79, 9.7%, [C
6
H
6
+H] ).
Á2H O: (637, 13.2%, [[NiL ](NO
2
2
+
try [31,34]. The energy of the band assigned to d–d transitions
can provide a rough estimate of the ligand field strength, since
one of the electronic transitions comprised in the band envelope
[NiL ](NO
3
)
] ),
2
2
3 2
) +H] ), (636, 20.2%,
2
+
2
+
[[NiL ](NO
3
)
2
(574,
8.1%,
[[NiL ](NO
3
)] ),
(573,
4.3%,
2
+
2
+
2
+
[[NiL ](NO
3
)ÀH] ), (514, 44.9%, [NiL +2H] ), (512, 67.9%, [NiL +H] ),
2
+
2
+
is d
0Dq-C [31,34]. The electronic spectra of the Ni(II) and Co(II)
complexes show an absorption band at 568–668 nm attributed
x
2-
y
2Àdxy and the energy associated with this transition is
(511, 100%, [NiL ] ), (498, 11.5%, [NiL -(O)+H] ), (483, 20.5%,
2
+
2
+
2
+
1
[NiL À(OCH
2
)] ), (456, 13.2%, [L +3H] ), (455, 29.1%, [L +2H] ), (454,
2
+
2
+
2
+
42.6%, [L +H] ), (439, 9.2%, [L À(CH
2
)] ), (423, 5.2%, [L À(OCH
2
)] ),
2
2
2
+
2
+
to the
E
g
? T2g transition, characteristic for tetragonally elon-
(419, 14.2%, [L À(OCH
2
CH
2
)] ), (405, 23.2%, [L À(OCH
2
CH
2
CH
2
)] ),
+
+
gated octahedral or square planar geometry [31,34]. The elec-
tronic absorption bands of the presented Ni(II) and Co(II)
complexes in the visible region exhibit solvent dependence
behavior. The observed red shifts in the low-energy d–d band of
Ni(II) and Co(II) complexes in DMF can be interpreted in terms
of weak ligand field strength [27,31,34].
(96, 8.2%, [C
6
H
6
O+2H] ), (79, 27.3%, [C
O: (637, 6.2%, [[CoL ](NO ) +H] ), (636, 22.9%,
2 3 2
] ), (635, 6.3%, [[CoL ](NO
6
H
6
+H] ).
2
2
+
[CoL ](NO
3
)
2
Á4H
2
+
2
+
2
[[CoL ](NO
3
)
2
3
)
2
ÀH] ), (574, 5.1%, [[CoL ]
+
2
+
2 +
(NO
3
)] ), (573, 2.3%, [[CoL ](NO
3
)ÀH] ), (514, 25.3%, [CoL +2H] ), (513,
2
+
2 + 2 +
47.9%, [CoL +H] ), (512, 61.3%, [CoL ] ), (498, 13.2%, [CoL À(CH
2
)] ),
2
)-H] ), (456,
2
+
2
+
(497, 7.2%, [CoL À(O)+H] ), (482, 10.3%, [CoL À(OCH
2
+
2
+
2
+
3
4.7%, [L +3H] ), (455, 62.1%, [L +2H] ), (454, 100%, [L +H] ), (439,
2
+
2
+
3.3. Magnetic studies
4.2%, [L À(CH
2
+
)] ), (423, 11.4%, [L À(OCH
2
)] ), (419, 14.2%,
2
+
+
[
L À(OCH
2 2 6 6 6 6
CH )] ), (96, 8.2%, [C H O+2H] ), (81, 2.3%, [C H +H] ), (80,
+
+
The metal–ligand mole ratio was found to be 1:1, according
9.1%, [C
6
1
H
6
+H] ), (79, 18.8%, [C
6 6
H +H] ).
to elemental analysis and mass spectra. Since all of the com-
plexes are paramagnetic, their NMR spectra could not be ob-
tained. The magnetic moments of the Cu(II) complexes carried
out at room temperature are in the range 2.02–2.17 BM, which
are typical for Cu(II) complexes having one unpaired electron
at this temperature. Magnetic susceptibility measurements pro-
vide sufficient data to characterize the structure of the Ni(II)
and Co(II) complexes. The magnetic moment measurements of
compounds were carried out at 25 °C. The magnetic moments
of the Ni(II) complexes carried out at room temperature are in
the range 2.64–2.81 B.M, which are typical for Ni(II) complexes
having two unpaired electron [31,34]. The room temperature
magnetic moment (3.78–3.96 B.M) determined for Co(II) metal
complexes, are close to the spin-only magnetic moment
[CuL ](NO O: See Figs. 3 and 5.
3
)
2
Á2H
2
4
. Conclusion
The novel six Schiff base macrocyclic complexes were prepared
and characterized by elemental analyses, FTIR and UV–vis spectra,
conductivity measurements, magnetic susceptibilities and mass
spectra. General structures of the complexes were shown in
Fig. 6. The Ni(II) and Co(II) complexes probability show tetrahedral
geometry and Cu(II) complexes probability show square planar
geometry around the central metal ions.
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l = 3.87 B.M) for three unpaired electrons. This result and the
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[
[
[
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3
.4. Conductivity measurements
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[
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.5. Mass spectra
The fragments observed in the mass spectrum of the complexes
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given below and shown in figures (Figs. 2–5).
[
[
1
1
+
[
NiL ](NO
3
)
2
Á2H
2
O: (622, 7.2%, [[NiL ](NO
3
)
2
+H] ), (621, 3.1%,
1
+
1
+
1
[
[NiL ](NO
3
)] ), (561, 5.4%, [[NiL ](NO
3
)+H] ), (560, 13.7%, [[NiL ]
+
1
+
1
+
(
NO
3
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[
1
+
1
+
1
+
1
8
00%, [NiL ] ), (441, 16.1%, [L +3H] ), (440, 46.1%, [L +2H] ), (439,
3.3%, [L +H] ), (438, 29.3%, [L +H] ), (424, 19.4%, [L À(CH
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Inorg. Chem. 25 (1986) 4260.
1
+
1
+
1
+
2
)] ),
+
+
(
[
96, 8.2%, [C
6
H
6
O+2H] ), (79, 27.3%, [C
Á3H O: see Figs. 2 and 4.
Á2H
6
H
6
+H] ).
[21] P. Comba, N.F. Curtis, G.A. Lawrance, M.A.O. Leary, B.W. Skelton, A.H. White, J.
Chem. Soc. Dalton Trans. (1988) 497.
1
[
[
CoL ](NO
3
)
2
2
[
22] L. Fabbrizzi, M. Licchelli, A.A.M. Lanfredi, O. Vassalli, F. Ugozzoli, Inorg. Chem.
5 (1996) 1582.
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1
+
CuL ](NO
3
)
2
+
2 3 2
O: (627, 11.3%, [[CuL ](NO ) +H] ), (626, 4.2%,
3
1
1
+
[CuL ](NO
3
)
2
] ), (625, 2.1%, [[CuL ](NO
3
)
2
ÀH] ), (624, 1.6%,

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