The novel triazine cored tripodal and trinuclear Schiff base-oxime metal complexes: Their magnetic properties and thermal decompositions

Article abstract of DOI:10.1002/jhet.671

Figure represented. 2,4,6-tris(4-hydroxybenzimino)-1,3,5-triazine [1, 2] (III) have been synthesized by the reaction of 1 equiv melamine and three equiv 4-hydroxybenzaldehyde, and characterized by means of elemental analysis, ¹H-NMR (nuclear ma

Full text of DOI:10.1002/jhet.671

936
The Novel Triazine Cored Tripodal and Trinuclear Schiff Base-
Oxime Metal Complexes: Their Magnetic Properties and Thermal
Decompositions
Vol 48
Sꢀaban Uysala* and Ahmet Coꢀskunb
aDepartment of Chemistry, Faculty of Science, Selcuk University, Konya 42031, Turkey
bDepartment of Chemistry, Faculty of Education, Selcuk University, Konya 42075, Turkey
*E-mail: uysal77@hotmail.com
Received June 14, 2010
DOI 10.1002/jhet.671
Published online 21 April 2011 in Wiley Online Library (wileyonlinelibrary.com).
2,4,6-tris(4-hydroxybenzimino)-1,3,5-triazine [1,2] (III) have been synthesized by the reaction of 1
equiv melamine and three equiv 4-hydroxybenzaldehyde, and characterized by means of elemental anal-
ysis, 1H-NMR (nuclear magnetic resonance spectroscopy), Fourier transform infrared (FTIR) spectr-
scopy, liquid chromatography-mass spectroscopy (LC-MS). L (IV) has been synthesized by the reaction
of one equiv (III) and three equiv 4-(thiophenoxy)phenyloxylohydroxymoyl chloride (II), and character-
ized by means of the same methods. Then, four novel trinuclear Fe(III) and Cr(III) complexes involving
tetradentate Schiff bases N,N0-bis(salicylidene)ethylenediamine-(salenH2) or bis(salicylidene)-o-phenyl-
enediamine-(salophen H2) with L (IV) have been synthesized and characterized by means of elemental
analysis, FTIR spectrscopy, LC-MS, thermal analyses. The metal ratios of the prepared complexes
have been determined using AAS. The aim of the present study is synthesis of novel
tridirectional-trinuclear systems and to present their effects on magnetic behavior of [salenFe(III)],
[salophenFe(III)], [salenCr(III)], and [salophenCr(III)] capped complexes. The complexes have also
been characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by keton-oxime group.
J. Heterocyclic Chem., 48, 936 (2011).
INTRODUCTION
many fields [10,11], such as supramolecular devices,
luminescent labels, fluorescent probes in biological and
medical applications, magnetic resonance imaging, and
catalytic cleavage of RNA, and they are also important
ligands [12] for recognizing inorganic and organic cati-
ons, anions, and neutral molecules.
1,3,5-Triazine derivatives are widely used as herbi-
cides [3], drugs [4], or polymers [5], like melamine
formaldehyde that has excellent thermal and electrical
properties [6]. An important class of compounds having
anticancer, antitumor, antiviral, and antifungal activity
consists of substituted 1,3,5-triazine (s-triazine) deriva-
tives. These macrocyclic compounds have been used in
the treatment of depression and hence gained a consider-
able importance. These are valuable bases for estrogen
receptor modulators [7] and also used as bridging agents
to synthesize herbicides and in the production of drugs
or polymers [8].
The great interest in synthetic macrocycles and mac-
roacycles and their corresponding metal complexes is
related to the fact that they can mimic naturally occur-
ring macromolecules in their structural features. The for-
mation of tripodal complexes depends significantly on
the dimension of the internal cavity, on the rigidity of
the ligand, on the nature of its donor atoms, and on the
complexing properties of the counterion. For tripodal
compounds, like podands, higher flexibility of arms and
Macrocyclic molecules present a multitude of new
properties [9] and open up vast vistas for applications in
C
V
2011 HeteroCorporation

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The Novel Triazine Cored Tripodal and Trinuclear Schiff Base-Oxime Metal Complexes:
Their Magnetic Properties and Thermal Decompositions
937
complexation ability grows with the ionic radius of vari-
ous metal ions [13].
Interest in the metal coordination environment has
prompted the study of oxime ligands due to their vari-
able geometries and the tunability of their substituents.
Oxime ligands are used as analytical reagents and serve
as models for biological systems (e.g. vitamin B12 and
dioxygen carriers) as well as catalysts in chemical proc-
esses [14].
Figure 1. The synthesis rotes for the preparation 4-(thiophenoxy)phe-
nyloxylo hydroxymoyl chloride.
The magnetochemical properties of the l-oxo-bridged
complexes [{Fe(salen)}2O] [(salenH2 ¼ N,N0-bis(salicy-
lidene) ethylenediamine)] and [{Fe(salophen)}2O] [(sal-
ophenH2 ¼ bis(salicylidene)-2-phenylenediamine)] and
their X-ray studies have widely been presented in the
literature [15–22]. Koc¸ and Ucan [23] have reported the
synthesis and characterization of 1,3,5-tricarboxylato
bridges with [salenFe(III)] and [salophenFe(III)]. Uysal
and Uc¸an have reported the synthesis and character-
ization of tricarboxylato triazine and tricatechol
triazine bridges with [salenFe(III)], [salophenFe(III)],
[salenCr(III)] and [salophenCr(III)] [24,25]. Uysal and
Koc¸ have also reported the synthesis and characteriza-
tion of dendrimeric carboxylato triazine bridges with
[salenFe(III)], [salophenFe(III)], [salenCr(III)], and [sal-
ophenCr(III)] [2]. Other complexes of composition
[{Fe(salen)}2L] (where L ¼ glutarate, adipate, pimelate,
suberate, and dithiooxamidedianion) were prepared by
Smekal et al. [26].
RESULTS AND DISCUSSION
The target ligands were synthesized in two-step from
melamine. The conversion of melamine to the trisubsti-
tuted-melamine derivative was accomplished in 71%
yield. The structural formula of L (IV) was verified by
elemental analyses, 1H-NMR, FTIR and mass spectral
data [2,25,33,34] (Figs. 1 and 2, Tables 1, 2). The ligand
is soluble in common organic solvents. Synthetic strat-
egy for preparing L uses a complex as a ‘‘ligand’’ that
contains a potential donor group capable of coordinating
to another ligand. Therefore, we choose [Fe(salen)]2O,
[Fe(salophen)]2O, [Cr(salen)]2O, and [Cr(salophen)]2O
as ‘‘ligand complex’’ [2,24,25,35]. These complexes are
some of the first examples of melamine-based trinuclear
complexes bridged to the iron/chromium centers by
keton and oxime groups. All compounds are stable at
room temperature in the solid state, and they are only
soluble in organic solvents such as ethylacetate, DMSO,
DMF, and insoluble in water. The results of the elemen-
tal analyses, given in Table 1, are in a good harmony
with the structures suggested for the ligands and their
complexes. The results show that all complexes are
trinuclear.
A
Schiff base complex of chromium(III),
[Cr(salen)(OH2)2]þ, was found to enhance insulin activ-
ity and insulin derivatized with the same was found to
exhibit higher activity in glucose metabolism in animal
models when compared to either free insulin or other
derivatives [27,28]. Their applications have grown rap-
idly. Various metal-salen complexes in the homogene-
ous phase such as manganese(III), chromium(III) and
nickel(II) salen have been used for the epoxidation of
olefins [29–32].
When 4-(thiophenoxy)phenyloxylohydroxymoyl chlo-
ride (II) was added to tripodal Schiff base ligand (III),
phenolic OH band at 3338 cmꢀ1 disappeared. The vibra-
tions of the triazine C¼¼N (a), azomethine C¼¼N (b),
oxime C¼¼N (c), C¼¼O and CAOAC of the free ligands
have been observed at 1579, 1628, 1598, 1654, and
1378 cmꢀ1, respectively, [32,35,36]. In the FTIR spectra
of (IV), the band at 3278 cmꢀ1 and 997 cmꢀ1 can be
assigned to the oxime- OAH and oxime NAO group
vibrations, respectively. IR bands at 1649 cmꢀ1 for
complex (V), 1653 cmꢀ1 for complex (VI), 1652 cmꢀ1
for complex (VII) and 1649 cmꢀ1 for complex (VIII)
were assigned to C¼¼N (c) streching vibrations, 1013,
1015, 1009, and 1008 cmꢀ1 were assigned to NAO
streching vibrations and band at 1536, 1538, 1540, and
1542 cmꢀ1 were assigned to C¼¼N (d) streching vibra-
tions for complexes (V), (VI), (VII), and (VIII), respec-
tively, whereas C¼¼N (d) streching vibration bands
werefound at 1560–1567 cmꢀ1 for [Fe(salen)]2O, [Fe
(salophen)]2O, [Cr(salen)]2O, and [Cr(salophen)]2O
The aim of this study is synthesis of novel tridirec-
tional-trinuclear systems and to present their effects on
magnetic behavior of [salenFe(III)], [salophenFe(III)],
[salenCr(III)], and [salophenCr(III)] capped complexes.
We also report that synthesized tridirectional melamine
Schiff bases present a new scaffold. The reaction of
melamine (C3N6H6) with 3 equiv of 4-hydroxybenzalde-
hyde in benzene produces the desired tris-iminophenol
in a single step under reflux, coded to be III. Then, the
reaction of III with 3 equiv of 4-(thiophenoxy)pheny-
loxylohydroxymoyl chloride (II) [33] in benzene in a
single step under reflux, codded to be L (IV). Their
structures were characterized by FTIR, 1H-NMR, LC-
MS, TGA-DTA, and magnetic suscebtibility. The metal
ratios of the prepared complexes have been determined
using AAS.
Journal of Heterocyclic Chemistry
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Sꢀ . Uysal and A. Coꢀskun
Vol 48
Figure 2. Synthetic routes for the preparation ligand IV and its metal complexes.
complexes [2,23,24,36–41]. In the the FTIR spectra of
tripodal-trinuclear complexes, oxime OH band disappears
and oxime NAO bands shift upward, suggesting chelation
of oxygen atoms to the metal. Bands at 1711, 1709,
1705, and 1710 cmꢀ1 for complexes (V), (VI), (VII), and
(VIII) were also assigned to C¼¼O groups since coordi-
nation of [Fe(salen)]2O, [Fe(salophen)]2O, [Cr(salen)]2O,
and [Cr(salophen)]2O to keton-oxime groups. In the tripo-
dal-trinuclear complexes, the bands in the 545–539 and
477–470 cmꢀ1 ranges can be attributed to the MAN and
MAO stretching modes [42].
To identify the structures of the ligands, the H-NMR
spectra were recorded in DMSO-d6. In the 1H-NMR
spectra of (III), the presence of singlet at d ¼ 6.08 ppm
1
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The Novel Triazine Cored Tripodal and Trinuclear Schiff Base-Oxime Metal Complexes:
Their Magnetic Properties and Thermal Decompositions
939
Table 1
Some physical properties, molecular weight (g/mol) data and elemental analyses, AAS analyses of the ligands and complexes.
Found (calculated) % of
lB B.M. M.p. Yield
Color MW
[g/mol]
Compounds
ꢂC
(%)
C
H
N
Fe
Cr
296 K
C24H18N6O6 (III)
C66H45N9O9S3 L (IV)
C114H90N15O15S3Fe3
L(FeSalen)3 (V)
–
–
142
234
72
62
66
White [438.45] 65.67 (65.75) 4.12 (4.14) 19.15 (19.17)
Orange [1204.34] 65,82 (65,64) 3.77 (3.68) 10.47 (10.31)
–
–
–
–
–
7.13 (7.71)
1.72
183a
Brown [2173.81] 61.45 (62.99) 3.94 (4.17)
Brown [2317.94] 63.57 (65.29) 3.11 (3.91)
Green [2162.26] 61.68 (63.33) 3.33 (4.20)
Green [2306.39] 64.71 (65.62) 3.28 (3.93)
8.73 (9.67)
8.23 (9.06)
8.54 (9.72)
8.34 (9.11)
C
C
C
126H90N15O15S3Fe3
L(FeSalophen)3 (VI)
114H90N15O15S3Cr3
L(CrSalen)3 (VII)
126H90N15O15S3Cr3
L(CrSalophen)3
(VIII)
1.75
3.69
3.74
191a
146a
155a
68
65
70
6.89 (7.23)
–
–
–
6.79 (7.21)
5.81 (6.76)
a Decomposition.
for three phenolic OH and singlet at d ¼ 9.77 ppm for
Mel–N¼¼CH-Ph-OH showed that three directional linked
to melamine had occurred [2]. Then, also 1H-NMR
spectra of confirmed the structures of the synthesized
compound L (IV) had seen that the value of OH chemi-
structures [43]. The magnetic moment value per metal
atom of trinuclear complexes which were constructed
from (IV) and one of these ligand complexes, [Fe(sa-
len)]2O, [Fe(salophen)]2O, [Cr(salen)]2O, and [Cr(salo-
phen)]2O, shows paramagnetic property with a magnetic
susceptibility value per atom at 296 K: 1.72–1.75 B.M.
[22] and 3.69–3.74 B.M., respectively. For Fe(III) com-
plexes such as (salen or salophen)Fe(III), magnetic
moments depend greatly upon the axial ligands. Many
literatures have reported that Fe(III) cores exhibit high
spin electronic structure (S ¼ 5ꢁ1/2), if only one ligand
donor oxygen atom coordinates to the Fe(III) cores of
salen or salophen complexes [44,45]. We reported here
that if keton-oxime groups coordinates to Fe(III) core of
salen or salophen complexes through its both oxygen
atoms, Fe(III) core exhibits low spin electronic structure
(S ¼ 1/2). That is, Fe(III) has the electronic structure of
1
cal shift disappeared [2]. The signal in H-NMR spec-
trum of (IV) at d 11.53 ppm correspond to the oxime –
OH proton resonances. The peak in H-NMR spectrum
1
of L (IV) at 10.00 ppm (singlet) correspond to the tria-
zine-CH¼¼N- proton resonances.
The magnetic moments of the complexes given in
Table 1 were measured at room temperature. On the
basis of spectral evidence, the Fe(III) and Cr(III) com-
plexes have trinuclear structures in which the Fe(III)
and Cr(III) cations have a nearly octahedral environ-
ment. The magnetic behavior of Fe(III) and Cr(III)
complexes is good harmony with proposed trinuclear
Table 2
Decomposition steps with the temperature range and weight loss for ligand and complexes.
Compound
Step no
Temp. range(ꢂC)
Weight loss found (calcd.) (%)
Fragmenta
CO, NO
C6H6, SH2
C6H6, CO2, H2O, N2
C6H6, C2H2, N2
CO, NO
C114H90N15O15S3Fe3 L(FeSalen)3 (V)
I
II
III
IV
I
183–286
314–382
490–623
664–787
191–295
323–397
506–648
679–792
146–221
286–356
424–563
671–790
155–232
291–368
435–576
669–784
10.63 (11.59)
23.47 (25.71)
34.68 (37.01)
19.12 (21.96)
9.34 (10.91)
22.83 (24.07)
37.41 (40.92)
17.96 (20.59)
9.82 (11.66)
22.91 (25.84)
35.41 (37.23)
18.32 (21.52)
8.97 (10.93)
23.11 (24.23)
38.93 (41.15)
18.03 (20.18)
C126H90N15O15S3Fe3 L(FeSalophen)3 (VI)
C114H90N15O15S3Cr3 L(CrSalen)3 (VII)
C126H90N15O15S3Cr3 L(CrSalophen)3 (VIII)
II
C6H6, SH2
III
IV
I
C6H6, CO2, H2O, N2
C6H6, C2H2, N2
CO, NO
II
C6H6, SH2
III
IV
I
II
III
IV
C6H6, CO2, H2O, N2
C6H6, C2H2, N2
CO, NO
C6H6, SH2
C6H6, CO2, H2O, N2
C6H6, C2H2, N2
a These are conjectural data.
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Sꢀ . Uysal and A. Coꢀskun
Vol 48
0
t2g5eg [23–25,39]. It is seen that the [Fe(salen)]2O,
[Fe(salophen)]2O, [Cr(salen)]2O, and [Cr(salophen)]2O
containing compounds are represented by the electronic
‘‘ligand’’ that contains a potential donor group capable
of coordinating to the other ligand. We have chosen
[Fe(salen)]2O, [Fe(salophen)]2O, [Cr(salen)]2O, and
[Cr(salophen)]2O as ‘‘ligand complexes’’ as they can
coordinate to the other ligand. These complexes are the
examples of tripodal-trinuclear complexes bridged by
ketoxime groups to the iron and chromium centers.
Their structures were characterized by means of elemen-
structure of t2g5eg and t2g3eg . The magnetic data for
the [Fe(salen)], [Fe(salophen)], [Cr(salen)], and [Cr(salo-
phen)] containing tripodal complexes show good
harmony with the low-spin d5 and d3 metal ion in an
octahedral structure. This consequence is supported by
the results of the elemental analyses suggesting that
these trinuclear complexes have also an octahedral struc-
ture [22,23,38–40,43,46].
0
0
1
tal analysis, H-NMR, FTIR spectrscopy, LC-MS, ther-
mal analyses, and magnetic susceptibility measurements.
The magnetic data for the tripodal-trinuclear complexes
show good harmony with the d5 and d3 metal ion in an
octahedral structure.
All the complexes have also been thermally investi-
gated in the range of 30–900ꢂC and their plausible degra-
tion schemes are presented in Table 2 [47,48]. Thermal
decomposition of the anhydrous [Fe(salen)], [Fe(salo-
phen)], [Cr(salen)], and [Cr(salophen)] complexes left
from the ligand (IV) have started in the range of the first
step 146–295. And, the anhydrous [Fe/Cr(salen or salo-
phen)] complexes detached from the ligand IV. The ther-
mal analyses (TG, DTA) of complexes V–VIII showed a
weight loss theoretically calculated to be 10.59–11.66%,
experimentally they were observed to be 8.97–10.63%,
respectively. It can be attributed that keton-oxime groups
decomposed in this step. At the second step was observed
in the range 286–397ꢂC. The thermal analyses (TG,
DTA) of complexes V–VIII showed a weight loss theo-
retically calculated to be 24.07–25.84%, experimentally
they were observed to be 22.83–23.47%, respectively. It
can be attributed that salen or salophen groups decom-
posed in this step. The third step was observed in the
range 424–648ꢂC. The thermal analyses (TG, DTA) of
complexes V–VIII showed a weight loss theoretically
calculated to be 37.01–41.15%, experimentally they were
observed to be 34.68–38.93%, respectively. It can be
attributed that diphenyltyoeter groups decomposed in this
step. And, the final decomposition step 664–794ꢂC. The
final decomposition products were metals and triazine
ring. The observed weight losses for all ligands and com-
plexes are in good harmony with the calculated values.
All ligand and complexes were investigated their LC-
MS (ESIþ) spectrum. The calculated molecular weights
of all ligand and complexes have been given in (Table
1). Molecular peaks of the cations are observed with the
same isotope distribution as the calculated ones, theoret-
ically. That is, from the investigation of LC-MS spectra
of the compounds, it has been seen that molecular
weights of ligands and complexes are in good harmony
with the intensity observed values in LC-MS spectra.
EXPERIMENTAL
General. Melamine, 4-hydroxybenzaldehyde and all other
reagents were purchased from Merck and used without further
purification. [Fe(salen)]2O, [Fe(salophen)]2O, [Cr(salen)]2O,
and [Cr(salophen)]2O were prepared according to previously
published methods [22,44,46]. 4-(Chloroacetyl)diphenyl-
thioether (I), 4-(thiophenoxy)phenyloxylo- hydroxymoyl
chloride (II), 2,4,6-tris(4-hydroxybenzimino)ꢀ1,3,5-triazine
(III) were synthesized according to previous reported methods
[2,33]. 1H-NMR spectra were taken using a Varian-Mercury
200 NMR spectrometer. The chemical shifts for NMR spectra
are ascribed in relation to the external TMS standard. IR spec-
tra were recorded using a Perkin-Elmer 1600 FTIR spectrome-
ter using KBr pellets. Elemental analyses were carried out
using a Hewlett-Packard 185 analyzer. Metal contents in com-
plexes were determined using Unicam 929 AAS spectrometer.
Mass spectra of the compounds were obtained on Varian MAT
711 spectrometer. pH values were measured on a WTW pH,
537 pH meter. Magnetic susceptibilities of metal complexes
were determined using a Sheerwood Scientific MX Gouy mag-
netic susceptibility apparatus carried out using the Gouy
method with Hg[Co(SCN)4] as calibrant. The effective mag-
netic moments, leff, per metal atom was calculated from the
pffiffiffiffiffiffi
expression: leff ¼ 2.84 vMT B.M., where vM is the molar
susceptibility.
The synthesis of L (IV). To a suspension of 2,4,6-tris(4-
hydroxybenzimino)ꢀ1,3,5-triazine (2.19 g, 5 mmol) and so-
dium carbonate (10.00 g) in 100 mL of benzene, stirred at
room temperature for 10 min, 3 equiv amount of 4-(thiophe-
noxy)phenyloxylohydroxymoyl chloride (4.38 g, 15 mmol) in
20 mL benzene was added. The mixture was refluxed for 120
h and then filtered. The participitate washed with hot ethylace-
tate, and the solvent mixture was evaporated under vacuum.
The benzene-ethylacetate solution of product was evaporated.
The product was purified using Colon Cromotography and
using 1:4 ethylacetate/n-hexane mixture as eluent. FTIR(cmꢀ1
)
3278 (OH), 2895 (CHar), 1579 (triazine C¼¼N a), 1628
(CH¼¼N b), 1598 (CH¼¼N c), 1654 (C¼¼O), 997 (NAO), and
1
CONCLUSIONS
1378 (CAOAC). H-NMR (DMSO-d6) d 11.53 (s, broad, 3H),
d 10.00 (s, 3H), 8.16 (dd, 12H, Ar-H, J 8.4, 4.3 Hz), 7.52–
7.46 (m, 21H), 7.29 (d, 6H, Ar-H, J 8.5 Hz). LC-MS data for
IV m/z: 1204 [100%, IV]. Molecular peaks of the cations are
observed with the same isotope distribution as the theoretical
In this study, novel tridirectional and melamine cored
Schiff bases III were synthesized. Synthetic strategy for
preparing tripodal-trinuclear uses
a complex as a
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The Novel Triazine Cored Tripodal and Trinuclear Schiff Base-Oxime Metal Complexes:
Their Magnetic Properties and Thermal Decompositions
941
[16] Coggon, P.; McPail, A. T.; Gross, P. M.; Mabbs, F. E.;
McLachlan, V. N. J Chem Soc A 1971, 1014.
[17] Dorfman, J. R.; Girerd, J. J.; Simhon, E. D.; Stack, T. D.
P.; Holm, R. H. Inorg Chem 1984, 23, 4407.
[18] Gerloch, M.; McKenzie, E. D.; Towl, A. D. C. J Chem Soc
A 1969, 2850.
ones. Some physical properties and yield for IV is given in
Table 1.
Preparation of L(FeSalen)3 (V), L(FeSalophen)3 (VI),
L(CrSalen)3 (VII) and L(CrSalophen)3 (VIII) complexes. A
solution of L (IV) (2.41 g, 2.0 mmol) and [Fe(salen)]2O or
[Cr(salen)]2O (3.0 mmol) or [Fe(salophen)]2O or [Cr(salo-
phen)]2O (3.0 mmol) in 50 mL of ethanol were refluxed for 20
h. The mixture was allowed to room temperature. Then the
mixture was filtered and dried in vacuum. LC-MS data, m/z:
2173 [100%, V], m/z: 2317 [100%, VI], m/z: 2162 [100%,
VII], and m/z: 2306 [100%, VIII]. Molecular peaks of the cat-
ions are observed with the same isotope distribution as the the-
oretical ones. Some physical properties and yield for V, VI,
VII, and VIII are given in Table 1. FTIR(cmꢀ1) for com-
plexes V: 2892 (CHar), 1571 (triazine C¼¼N a), 1633 (CH¼¼N
b), 1649 (C¼¼N c), 1536 (C¼¼N d), 1711 (C¼¼O), 1013
(NAO), 1376 (CAOAC), 539 (MAN), 476 (MAO), for com-
plexes VI: 2890 (CHar), 1568 (triazine C¼¼N a), 1629 (CH¼¼N
b), 1653 (C¼¼N c), 1538 (C¼¼N d), 1709 (C¼¼O), 1015
(NAO), 1379 (CAOAC), 541 (MAN), 477 (MAO), for com-
plexes VII: 2889 (CHar), 1572 (triazine C¼¼N a), 1631
(CH¼¼N b), 1652 (C¼¼N c), 1540 (C¼¼N d), 1705 (C¼¼O),
1009 (NAO), 1380 (CAOAC), 545 (MAN), 470 (MAO), for
complexes VIII: 2888 (CHar), 1570 (triazine C¼¼N a), 1627
(CH¼¼N b), 1649 (C¼¼N c), 1542 (C¼¼N d), 1710 (C¼¼O),
1008 (NAO), 1382 (CAOAC), 541 (MAN), 476 (MAO).
[19] Elmali, A.; Atakol, O.; Svobodaand, I.; Fuess, H. Z Kristal-
logr 1993, 203, 275.
[20] Kamenicek, J.; Travnicek, Z.; Sindelar, Z.; Walla, J. Pol J
Chem 1996, 70, 854.
[21] Marek, J.; Smekal, Z.; Travnicek, Z. Acta Univ Palacki
Olomuc Fac Rerum Nat 1996, 35, 33.
[22] Kopel, P.; Sindelar, Z.; Klicka, R. Transit Metal Chem
1998, 23, 139.
[23] Koc¸, Z. E.; Uc¸an, H. I. Transit Metal Chem 2007, 32, 597.
[24] Uysal, Sꢀ.; Uc¸an, H. I. J Incl Phenom Macrocycl Chem
2009, 65, 3, 209.
[25] Uysal, Sꢀ.; Uc¸an, H. I. J Incl Phenom Macrocycl Chem
2009, 65, 3, 403.
[26] Smekal, Z.; Brezina, F.; Sindelar, Z.; Klicka, R. Transit
Metal Chem 1996, 21, 49.
[27] Govindaraju, K.; Ramasami, T.; Ramaswamy, D. J Inorg
Biochem 1989, 35, 127.
[28] Shrivastava, H. Y.; Devaraj, S. N.; Nair, B. U. J Inorg Bio-
chem 2004, 98, 387.
[29] Srinivasan, K.; Michaud, P.; Kochi, J. K. J Am Chem Soc
1986, 108, 2309.
[30] Samsel, E. G.; Srinivasan, K.; Kochi, J. K. J Am Chem Soc
1985, 107, 7606.
[31] Yoon, H.; Burrows, C. J. J Am Chem Soc 1988, 110, 4087.
[32] Luts, T.; Frank, R.; Suprun, W.; Fritzsche, S.; Hey-Haw-
kins, E.; Papp, H. J Mol Catal A: Chemical 2007, 273, 250.
[33] Coꢀskun, A.; Karapinar, E. J Incl Phenom Macrocycl Chem
2008, 60, 59.
REFERENCES AND NOTES
[1] Akopova, O. B.; Shabyshev, L. S.; Kotovich, L. N.; Pankra-
tova, N.V. Russ J Physic Chem 1996, 70, 421.
[2] Uysal, Sꢀ.; Koc¸, Z. E. J Hazard Mater 2010, 175, 532.
[3] Carmouna, M.; Blanchoud, H.; Teil, M. J.; Blanchard, M.;
Chevreuil, M. Water Air Soil Pollut 2001, 132, 1.
[4] Klenke, B.; Stewart, M.; Barrett, M.; Brun, R.; Gilbert, I.
H.;J Med Chem 2001, 44, 3440.
[34] Tahmassebi, D. C.; Sasaki, T. J Org Chem 1994, 59, 679.
[35] Yang, G. M.; Liao, D. Z.; Jiang, Z. H.; Yan, S. P.; Wang,
G. L. Transit Metal Chem 1998, 23, 313.
[36] Karatas, I.; Ucan, H. I. Synth React Inorg Met-Org Chem
1998, 28, 383.
[5] Patel, H. S.; Patel, V. C. Eur Polym J 2001, 37, 2263.
[6] Hoog, P.; Gamez, P.; Lu¨ken, M.; Roubeau, O.; Krebs, B.;
Reedijk, J. Inorg Chim Acta 2004, 357, 213.
[37] Ucan, H. I.; Karatas, I.; Irez, G.; Deveci, M. A.; Mercimek,
B. Synth React Inorg Met-Org Chem 1998, 28, 3, 331.
[38] Kessel, S. L.; Hendrickson, D. N. Inorg Chem 1978, 17,
2630.
[7] Sirivinas, K.; Sirivinas, U.; Jayathirtha, R.; Bhanuprakasf,
K.; Kishore, K. H.; Murty, U. S. N. Bioorg Med Chem Lett 2005, 15,
1121.
[39] Uysal, Sꢀ.; Coꢀskun, A.; Koc¸, Z. E.; Uc¸an, H. I. J Macromol
Sci A 2008, 45, 727.
[8] Hoog, D. P.; Gamez, P.; Dressen, W. L.; Reedijk, J. Tetra-
hedron Lett 2002, 43, 6783.
[40] Koc¸, Z. E.; Uc¸an, H. I. J Macromol Sci A 2008, 45, 1072.
[41] Parekh, J.; Inamdhar, P.; Nair, R.; Baluja, S.; Chanda, S. J
Serb Chem Soc 2005, 70, 1155.
[9] Lehn, J. M. Acc Chem Res 1978, 11, 49.
[10] Bradshaw, J. S.; Krakowiak, K. E.; An, H. Y.; Wang, T.
M.; Zhu, C. Y.; Izatt, R. M. Tetrahedron Lett 1992, 33, 4871.
[11] Yu, S. Y.; Wang, Q. M.; Wu, B.; Wu, X. T.; Hu, H. M.;
Wang, L. F.; Wu, A. X. Polyhedron 1997, 16, 321.
[12] Ragunathan, K. G.; Bharadwaj, P. K. Tetrahedron Lett
1992, 33, 7581.
[42] Khalil, S. M.; Emara, A. A. J Coord Chem 2002, 55, 17.
[43] Dotson, D. L. PhD. Dissertation, Virginia Polytechnic Insti-
tute and State University, Virginia, 1996.
[44] Kopel, P.; Sindelar, Z.; Biler, M.; Klicka, R. Pol J Chem
1998, 72, 9, 2060.
[13] Leniec, G.; Kaczmarek, S. M.; Typek, J.; Ko1odziej, B.;
Grech, E.; Schilf, W. Solid State Sci 2007, 9, 267.
[14] Llanguri, R.; Morris, J. J.; Stanley, W. C.; Bell-Loncella, E.
T.; Turner, M.; Boyko, W. J.; Bessel, C. A. Inorg Chim Acta 2001,
315, 53.
[45] Kopel, P.; Biler, M.; Travnieek, Z.; Nadvornik, M. Acta Univ
Palackianae Olomucensis Facul Rerum Natural Chimica, 1998, 37, 17.
[46] Gembicky, M.; Boca, R.; Renz, F. Inorg Chem Comm
2000, 3, 662.
[47] El-Metwally, N. M.; Gabr, I. M.; El-Asmy, A. A. Transit
Metal Chem 2006, 31, 71.
[15] Ashmawy, F. M.; Ujaimi, A. R.; McAuliffe, C. A.; Parish,
R. V.; Pritchard, R. G. Inorg Chim Acta 1991, 187, 155.
[48] Brzyska, W.; Krol, A. Thermochim Acta 1993, 223, 241.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet