Nanodimensional microreactors encapsulation of 15- and 16-membered diaza dioxa macrocyclic Schiff-base copper(II) complex nanoparticles: Synthesis and characterization

Article abstract of DOI:10.1016/j.inoche.2009.11.028

Copper(II) complexes with 15- and 16-membered diaza dioxa Schiff-base macrocyclic ligands "[Cu(R[15 or 16]N₂O₂)]²⁺ (R = Et, Pr, Ph, Ch)" were entrapped in the nanopores of zeolite-Y by a three-step process in the liquid ph

Full text of DOI:10.1016/j.inoche.2009.11.028

Inorganic Chemistry Communications 13 (2010) 266–272
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Nanodimensional microreactors encapsulation of 15- and 16-membered diaza
dioxa macrocyclic Schiff-base copper(II) complex nanoparticles: Synthesis
and characterization
Masoud Salavati-Niasari *
Institute of Nano Science and Nano Technology, University of Kashan, Kashan, P.O. Box 87317-51167, Islamic Republic of Iran
Department of Chemistry, University of Kashan, Kashan, P.O. Box 87317-51167, Islamic Republic of Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 July 2009
Accepted 30 November 2009
Available online 3 December 2009
Copper(II) complexes with 15- and 16-membered diaza dioxa Schiff-base macrocyclic ligands ‘‘[Cu(R[15
or 16]N O )] (R = Et, Pr, Ph, Ch)” were entrapped in the nanopores of zeolite-Y by a three-step process in
2 2
2+
the liquid phase: (i) exchange of Cu(II) ions with NaY in water solution, (ii) reaction of Cu(II)–NaY with
excess 1,3-bis(2-carboxyaldehydephenoxy)propane (O ) in methanol, [(1,3-bis(2-carboxyaldehyde-
2 2
O
phenoxy)propane)copper]2 @NaY, [Cu(O
+
O )] @NaY (iii) template synthesis of [Cu(O O )] @NaY with
2 2 2 2
2+
2+
Keywords:
diamine. The obtained new complex nanoparticles entrapped in the nanopores of zeolite Y have been
characterized by elemental analysis FT-IR, XPS, DRS, UV–vis spectroscopic techniques, molar conduc-
tance, magnetic moment data, XRD and nitrogen adsorption. Analysis of data indicates all of the com-
plexes have been encapsulated within nanopores without affecting the zeolite framework structure.
Ó 2009 Elsevier B.V. All rights reserved.
Complex nanoparticles
Zeolite encapsulation
Copper(II)
Nanocomposite materials
Complex nanoparticles entrapped in the nanopores of zeolite Y
are fascinating class of materials, which have attracted wide spread
attention in basic science as well as technology development.
Zeolites are endowed with unique physical and chemical charac-
terization, which offers opportunities to manipulate active site
microenvironment. They are even compared with the catalytic
antibodies and metallo-enzymes and hence they are often referred
to as zeozymes [1,2]. Some of the prominent physical characteris-
tics of zeolites are their ruggedness to temperature and pressure
and their ability to recognize, discriminate and organize molecules
with less than 0.1 nm levels precision at the active site [3]. More-
over, non corrosive, environment friendly and economically viable
nature of the zeolite catalyzed reactions have provided the oppor-
tunity for the development of various industrial processes such as
fluid catalytic cracking, hydrocracking, isomerization and oxida-
tion. Zeolites are crystalline aluminosilicates whose internal voids
are formed by cavities and channels of strictly regular dimensions
and of different sizes and shapes. In particular, the pore structure
of Y zeolite consists of almost spherical 1.3 nm cavities intercon-
nected tetrahedrally through smaller apertures of 0.74 nm diame-
ter. The metal complex can be easily accommodated inside the
supercages of Y zeolite. Over the last decade, there has been a
dramatic increase in synthesis, characterization and application
of novel nanoporous materials [4–18].
In the continuation of previous works, I decided to prepare 15-
and 16-membered diaza dioxa macrocyclic ligand encapsulated
within nanopores of zeolite-Y. To the best of my knowledge, this
is the first report about synthesis of encapsulated 15- and 16-
membered diaza dioxa macrocyclic ligand. In this research, has
been shown that the macrocyclic complexes can be synthesized
via two steps within nanopores of zeolite-Y. With this applied
strategy, other macrocyclic compound could be encapsulated with-
in zeolite-Y.
In this paper, has been reported the synthesis and characteriza-
tion of copper(II) complexes of 15- and 16-membered diaza dioxa
macrocyclic ligand ‘‘Et[15]N
dibenzo[b,h][1,10,4,7]dioxadiazacyclotridecine, Pr[16]N
15,16,17,18-hexahydro-6H,14H-dibenzo[b,I][1,11,4,8]dioxadiaza-
cyclotetradecine, Ph[15]N 5,12,13,19-tetrahydro-11H-tribe-
nzo[b,e,h][1,10,4,7]dioxadiazacyclotridecine, Ch[15]N : 1,2,3,
2
O
2
:
5,6,7,8,15,16-hexahydro-14H-
2 2
O :
7,8,
2 2
O :
2
O
2
4,4a,5,12,13,19,19a-decahydro-11H-tribenzo[b,e,h][1,10,4,7]diox-
adiazacyclotridecine” encapsulated within the nanopores of
zeolite-Y by the template condensation of diamine and [(1,3-
2
+
bis(2-carboxyaldehydephenoxy)propane)copper] , [Cu(R[15 or
2
+
1
2 2
6] N O )] @NaY, shown in Schemes 1 and 2. Instrumental details
for elemental analysis, IR, TGA, XRD, XPS, BET spectroscopy were
the same as described earlier [19–22].
*
Address: Institute of Nano Science and Nano Technology, University of Kashan,
Kashan, P.O. Box 87317-51167, Islamic Republic of Iran. Tel.: +98 361 5555333;
fax: +98 361 5552930.
[
Cu(R[15]N
2
O
2
4
)](ClO )
2 2
ꢀ2H O and copper(II) complex nanopar-
E-mail address: salavati@kashanu.ac.ir
ticles entrapped in the nanopores of zeolite Y, [Cu(R[15 or
1
387-7003/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2009.11.028

M. Salavati-Niasari / Inorganic Chemistry Communications 13 (2010) 266–272
267
Scheme 1. 15-, and 16-membered diaza dioxa macrocyclic copper(II) complexes.
H
H
O
O
Cu(ClO4)2 6H O
2
.
O
O
O
O
Br
Br
OH
HO
H
H
NH2
NH2
H N
H N
NH2
2
2
H N
2
H N
NH2
2
O
N
O
O
O
O
O
O
O
Cu 2+
Cu2+
Cu 2+
Cu2+
N
N
N
N
N
N
N
H
H
H
H
H
H
H
H
2
+
2+
2
+
[Cu(Ph[15]N O )]
2+
[Cu(Pr[16]N O )]
[Cu(Et[15]N O )]
2 2
[
Cu(Ch[15]N O )]
2
2
2
2
2
2
Scheme 2. Reaction mechanism of 15-, and 16-membered diaza dioxa macrocyclic copper(II) complexes.
1
6]N
2
O
2
)]2+@NaY (R = Et, Pr, Ph, Ch) were prepared according to
ysis, mass and FT-IR spectrometry. The mass spectrum of com-
plexes plays an important role in confirming the monomeric
[1 + 1] (dialdehyde and diamine) nature of complexes [34]. All
mass spectra showed molecular ion peaks for the 1:1 metal-to-li-
gand stoichiometry with no further peaks above them. The
Ref. [23]. In this study, the [1 + 1] macrocycle Schiff-base
complexes were prepared as the major product by the reaction
dialdehyde and copper(II) perchlorate with diamines in methanol.
The macrocyclic complexes were characterized by elemental anal-

2
68
M. Salavati-Niasari / Inorganic Chemistry Communications 13 (2010) 266–272
copper(II) complexes are extremely stable in the solid state and in
the solution media, these complexes are relatively stable against li-
gand dissociation in highly acidic solution. The crystals were
unsuitable for single-crystal X-ray structure determination and
are insoluble in most common solvents, including water, EtOH,
compounds to the copper(II) center through the two nitrogen
and two oxygen atoms (N ) are expected to reduce the electron
density in the azomethine link and hydroxyl group. The spectra of
all the copper(II) complexes are dominated by bands between
2 2
O
ꢁ
1
ꢂ2940 cm due to
t
(Alph.–CH) groups. A new band appearing
in the ꢂ1194 cm region was assigned to (R–O) mode [26]. The
stretching vibrations (Ar–C@C) show a very strong band in the
1490–1490 and 1456–1458 cm
the bonding is also shown by the observation that new bands in
ꢁ
1
2 3 2
Et O, CH Cl, CH Cl
, C H
2 2 5
3 3
OOCCH , and CH CN.
t
A preliminary identification of the copper complexes was made
t
ꢁ
1
on the basis of their IR spectra, which exhibited no bands charac-
teristic of free primary amine, thus supporting the proposed mac-
rocyclic skeleton (Scheme 1). The copper(II) complexes, [Cu(R[15
range. Conclusive evidence of
ꢁ
1
the IR spectra of the copper(II) complexes appear at ꢂ460 cm
ꢁ1
2
or 16]N O
2
)](ClO
4
)
2
, readily dissolve in DMF and DMSO. The overall
and ꢂ350 cm assigned to
t(Cu–O) and t(Cu–N) stretching vibra-
geometries of all macrocycles have been deduced on the basis of
the observed values of the magnetic moments and the band posi-
tions in the electronic spectra [34]. Magnetic studies and conduc-
tivity measurements. The metal-ligand mole ratio was found to
be 1:1, according to elemental analysis. Since all of the copper(II)
complexes are paramagnetic, their NMR spectra could not be ob-
tained. Magnetic susceptibility measurements provide sufficient
data to characterize the structure of the metal complexes. The cop-
per(II) complexes are 2:1 electrolytes as shown by their molar con-
tions. Thus, from the IR spectra it is clear that the compounds are
bonded to the copper ion in a tetradentate fashion through the
deprotonated phenolate oxygen and aldimine nitrogen (Scheme
1). Also, infrared spectra of the copper(II) complexes exhibit an in-
ꢁ1
tense band approximately between 1182 and 1110 cm
along
with a weak band at between 651 and 625 cm which have been
assigned to the perchlorate complexes due to (Cl–O) of uncoordi-
ꢁ1
t
nated perchlorate anions [27]. The IR bands of all encapsulated
complex nanoparticles were weak due to their low concentration
in the zeolite. Cu(II) complex nanoparticles encapsulated in the
zeolite cages did not show any significant shift in C@N stretching
modes. We did not notice any appreciable changes in the frequen-
cies of copper(II) complexes after incorporation into zeolite matrix.
The UV–vis spectral data for the metal complexes are given in
Experimental section. The electronic spectra of copper(II) com-
plexes in DMF show four peaks in the UV–vis. region. The absorp-
ꢁ
3
ductivities (
K
) in DMF at 10 M, which are in the range 170–
ꢁ
1
2
ꢁ1
1
80
X
cm mol . The molar conductivities of the compounds
in DMF are the range reported for 2:1 electrolytes (Scheme 2).
The percentage of copper contents determined before and after
encapsulation by inductively coupled plasma (ICP) along with their
expected formula is presented [34]. As crude mass was extracted
with methanol, the metal ion content found after encapsulation
is only due to the presence of metal complexes in the nanopores
of the zeolite-Y. The molecular formula of the complex nanoparti-
tion bands below 290 nm are practically identical and can be
*
p ? p transitions in the benzene ring and azome-
attributed to
2
+
cles are based on the neat complexes [Cu(R[15 or 16]N
2
O
2
)] that
thine groups. The absorption bands observed within the
*
have also been prepared and characterized. Synthesis of copper(II)
complex nanoparticles encapsulated in the nanopores of zeolite-Y
involves three steps: (i) exchange of Co(II) ions with NaY in water
ꢂ335 nm are most probably due to the transitions of n ?
p of
imine groups [28]. The general character of these spectra is very
similar to that of the corresponding complexes of unsymmetrical
disubstituted phenoxy groups. This is probably due to the fact that
metal-to-ligand charge transfer and ligand-to-metal charge trans-
fer transitions have similar energy differences [29]. The visible
2 2
solution, (ii) reaction of Cu(II)–NaY with excess dialdehyde (O O )
2+
in methanol (iii) reaction of [Cu(O
2
O
2
)] –NaY with diamine
(
1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene or
2
+
1
,2-diaminocyclohexane) where diamine slowly enters into the
spectra of the [Cu(R[15 or 16]N
2 2
O )] complex consists of a max-
nanopores of zeolite-Y due to its template nature and interacts
imum or a broad shoulder around 608 nm, which can be assigned
2
+
2
2
with [Cu(O
2
O
2
)] ions (Scheme 3). Soxhlet extraction using etha-
2
to the E ? T . The magnetic moment for the former complex is
nol and chloroform finally purified the impure complexes. The
remaining un-complexed metal ions in zeolite were removed by
exchanging with aqueous 0.01 M NaCl solution. As one extra anio-
nic ligand would be required to balance the overall charges on the
1.93 B, which may be due to either tetrahedral or square planar
l
structure [30,31]. The diffuse reflectance spectra of copper(II) com-
plexes contain diaza dioxa macrocycle were almost identical be-
fore and after encapsulation, indicating the complexes maintain
their geometry even after supported without significant distortion.
These data compare closely with that of pure complexes as well as
of encapsulated complexes and are indicative of a tetrahedral
structure present within the nanodimensional pores of zeolite.
The X-ray diffraction (XRD) patterns of encapsulated complexes
are shown in Fig. 1. The encapsulated complex exhibit similar
peaks to those of zeolite Y, except for a slight change in the inten-
sity of the peaks, no new crystalline pattern emerges. These facts
confirmed that the framework and crystallinity of zeolite were
not destroyed during the preparation, and that the complexes were
well distributed in the cages. The relative peak intensities of the
220, 311 and 331 reflections have been thought to be correlated
to the locations of cations. In zeolite Y, the order of peak intensity
is in the order: I331 ꢃ I220 > I311, while in encapsulated complexes,
the order of peak intensity became I331 ꢃ I311 > I220. The difference
ꢁ
Cu(II), Cl of NaCl used during exchanged process fulfills this
requirement. Thus, the formula of copper(II) complex may be
2+
written as [Cu(R[15 or 16]N
has Si/Al molar ratio of 2.53 which corresponds to a unit cell
formula Na56[(AlO 56(SiO 136]. The unit cell formula of metal-ex-
changed zeolites shows 10.8 moles of copper dispersion per unit
cell (Na34Co10.8[(AlO 56(SiO O). Metal ion exchange at
136]ꢀnH
2 2
O )] @NaY. The parent NaY zeolite
2
)
2
)
2
)
2
)
2
around 36% leads to 2.81–2.87% of metal loading in zeolite. The
CHN analysis results of the neat copper complexes showed near
similarity to the theoretical values. The copper contents of the
zeolite encapsulated samples were estimated by dissolving known
amounts of the catalyst in concentric HCl and using AAS. The ana-
lytical data of each complex indicate molar ratios of Cu:C:H almost
close to those calculated for the mononuclear structure [34].
FT-IR spectra of copper(II) complexes were recorded in KBr pel-
ꢁ
1
2+
let from 4000 to 400 cm . The infrared spectra of copper(II) com-
plexes have been studied in order to characterize their structures.
indicates that the ion-exchanged Cu , which substitutes at the
+
location of Na , undergoes rearrangement during complexation.
ꢁ1
The broad bands within the ꢂ3334 cm range for all copper(II)
The surface area and pore volume of the materials are studied
2
+
complexes can be attributed to stretching vibrations of water mol-
2 2
[34]. The encapsulation of [Cu(R[15 or 16]N O )] complexes in
ecule
copper(II) complexes in the ꢂ1615 cm region which is attributed
to the (C@N) stretch, indicating coordination of the azomethine
nitrogen to copper metal [25]. Coordination of the Schiff-base of
t
(H
2
O) [24]. A strong band observed in the IR spectra of the
zeolite reduced the adsorption capacity and the surface area of
the zeolite. The lowering of the pore volume and surface area indi-
cated the presence of complexes within the zeolite nanocages and
not on the external surface.
ꢁ1
t

M. Salavati-Niasari / Inorganic Chemistry Communications 13 (2010) 266–272
269
=
Cu(II)
NaY
Cu(II)-NaY
Ar
O
O
O
O
H
H
O
H N
NH2
2
H
O
N
N
H
H N
2
O
O
O
O
H N
2
H
H
[
Cu(Et[15]N O )]2+@NaY
2
2
NH2
NH2
NH2
NH2
O
N
O
N
H
H
O
N
O
N
H
H
O
O
N
N
H
H
[
Cu(Pr[16]N O )]2+@NaY
2 2
[
Cu(Ph[15]N O )]2+@NaY
2 2
[
Cu(Ch[15]N O )]2+@NaY
2 2
Scheme 3. Encapsulation of copper(II) complex nanoparticles of 15-, and 16-membered diaza dioxa Schiff-base within nanopores of zeolite-Y.
Thermal stability of as-prepared compound was investigated by
thermogravimetric analysis (TGA). The thermal decomposition of
all these materials such as: [Cu(R[15 or 16]N O )] @NaY occurs
2 2
in two steps (see Fig. 2). First step starts shortly after increasing
the temperature above 150 °C and continues until the loss of all
intrazeolite water. Second step occurs in a wide temperature range
(200–450 °C) and is due to the slow decomposition of the chelating
ligand. A very small weight percentage loss indicates the presence
of only small amount of metal complex insertion in the nanopores
of the zeolite. This is in agreement with the low percentage of me-
2+

2
70
M. Salavati-Niasari / Inorganic Chemistry Communications 13 (2010) 266–272
Fig. 1. XRD patterns of NaY, Cu2+@NaY, [Cu(Et[15]N )]2+@NaY, [Cu(Pr[16]N )]2+@NaY, [Cu(Ph[15]N )]2+@NaY and [Cu(Ch[15]N )]2+@ NaY.
O O O O
2 2 2 2 2 2 2 2
ratios of NaY and of modified samples were similar, which indi-
cates that de-alumination does not occur during the encapsulation
procedure. The binding energies of the elements detected by XPS
are summarized. The most intense bands identified are due to
the zeolite structure, in the Si 2p region a band at 103.5 eV typical
for Si atoms with different chemical environments, such as SiO
and terminal Si–OH groups. In the Al 2p region a band at 75.1 eV
from the tetrahedral AlO groups and a symmetrical large band
4
4
at 531.0 eV from the O 1s region, and finally a band in the Na 1s
region at 1072.6 eV were also observed [34]. The amount of surface
copper is very similar to the bulk copper content, which that sug-
gests the complex nanoparticles are homogeneously distributed
throughout the NaY crystals. The medium binding energy values
for Cu 2p3/2 are different before and after encapsulation, which
indicates the change in environment of the copper upon coordina-
tion with the macrocyclic ligand. Before coordination the medium
binding energy of Cu 2p3/2 value is 934.0 eV (Cu(II)@NaY) and after
the complex encapsulation the value is 935.8 eV, [Cu(Et[15]-
Fig. 2. TGA profiles of NaY, Cu2+@NaY and [Cu(Et[15]N )]2+@NaY.
O
2 2
2+
2+
N
2
O
2
)] @NaY, 935.6 eV, [Cu(Pr[16]N
2
O
2
)] @NaY, 936.1 eV,
+
2+
[
Cu(Ph[15]N
2
O
2
)]2 @NaY and 935.9 eV, [Cu(Ch[15]N
2
O
2
)] @NaY
(
Table 1). These results confirm the same copper coordination
tal content estimated by atomic absorption spectrometer. Com-
pared to the neat complex, the decomposition of the zeolite-encap-
sulated complex nanoparticles occurs at the higher temperature. A
similar enhancement of the thermal stability of a metal complex
on encapsulation has been observed earlier [32].
The presence of the complex in NaY was supported by XPS anal-
ysis. All modified NaY samples revealed the presence of oxygen, so-
dium, silicon and aluminium from the zeolite lattice in their XPS
resolution spectra. The bands typical of the copper(II) complex,
scarcely visible because of their low loading, were identified in
the Cu 2p3/2 and N 1s region. The bulk and the surface Si/Al atomic
sphere for the complex when free or encapsulated within NaY zeo-
lite and that the host matrix environment does not affect the va-
lence state of the metal atom of the complex. The high resolution
C 1s spectrum of encapsulated complexes shows an asymmetric
band centered at 285.0 eV that can be de-convoluted into three
individual bands. The three bands at high energy were also ob-
served in the starting material and are presumably due to the pres-
ence of some contamination. The band at 289.1 eV is attributed to
the aromatic carbons ligand. The encapsulated complexes and the
free complex samples exhibit in the N 1s region a band centered at
Table 1
2 2 2 2 2 2 2 2
XPS data of NaY, Cu@NaY, [Cu(Et[15]N O O O O
)]2+@NaY, [Cu(Pr[16]N )]2+@NaY, [Cu(Ph[15]N )]2+@NaY and [Cu(Ch[15]N )]2+@ NaY.
Sample
Si(2p) (eV)
Al(2p) (eV)
Na(1s) (eV)
C(1s) (eV)
O(1s) (eV)
Si/Al (eV)
Cu 2p3/2 (eV)
NaY
Cu@NaY
Cu(Et[15]N
103.5
103.5
103.6
103.6
103.6
103.6
75.1
75.1
75.1
75.1
75.1
75.1
1072.6
1072.6
1072.6
1072.7
1072.8
1072.7
285.0
285.0
285.0
285.0
285.0
285.0
531.0
532.5
532.7
532.8
532.9
532.7
2.61
2.58
2.58
2.58
2.58
2.58
–
934.0
935.8
935.6
936.1
935.9
2 2
O
)]2 @NaY
+
2+
[Cu(Pr[16]N
[Cu(Ph[15]N
[Cu(Ch[15]N
2 2
O )] @NaY
2 2
O
)]2 @NaY
+
2
+
2 2
O )] @NaY

M. Salavati-Niasari / Inorganic Chemistry Communications 13 (2010) 266–272
271
4
00.6, due to the contribution of nitrogen atoms of the ligand. Cop-
(0.025 M). The mixture was then heated while stirring at 90 °C for 24 h. The
solid was filtered, washed with hot distilled water till the filtrate was free from
any copper(II) ion (by AAS of filtrate) content and dried for 10 h at 80 °C under
vacuum. The ionic exchange degree was determined by atomic absorption
spectrophotometer. Typically a 4 g sample of Cu(II)–NaY zeolite was mixed
with 1.60 g of [1,3-bis(2-carboxyaldehydephenoxy)propane] suspended in
per remains in the 2+ oxidation state in encapsulated complexes
and it matches well with the reported values for similar systems
[
33].
In summary, the diaza dioxa macrocyclic complex nanoparti-
100 ml of methanol and then refluxed for 8 h. The solid consisting of
2+
cles, [Cu(R[15 or 16]N
sulated in the nanopores of zeolite by template condensation
between pre-entrapped, [Cu(O
carboxyaldehydephenoxy)propane)] complex with diamine,
2 2
O )] (R = Et, Pr, Ph, Ch), have been encap-
dialdehyde coordinated with Cu(II) in Cu(II)–NaY and denoted as
2+
2 2
[Cu(O O )] @NaY was collected by filtration, washed with methanol. The
2+
resulted zeolites, were Soxhlet extracted with chloroform (for 4 h) and then
with ethanol (for 3 h) to remove excess unreacted dialdehyde and any
copper(II) complexes adsorbed onto the external surface of the zeolite
crystallines. The resulting solids were dried at 70 °C under vacuum for
2 2 2 2
O )] @NaY (O O = [1,3-bis(2-
2
+
[
Cu(N
2 2 2
O -N) ] @NaY. This strategy appears to be effective for
2
4 h.Preparation of complex nanoparticles entrapped in the nanopores of zeolite Y:
the encapsulated of Cu(II) complexes with 15-, 16-membered diaza
dioxa macrocycle ligands derived from [CuO
plate condensation in the nanopores is still possible and no unre-
acted [CuO
spectroscopic data suggest that the encapsulated complex nano-
particle experience very little distortion in the supercage and that
the chemical ligation to the zeolite surface is minimal. The new
complex nanoparticles entrapped in the nanopores of zeolite Y
2+
2+
2 2
To a stirred methanol suspension (100 ml) of [Cu(O O )] @NaY (2 g) were
2 2
O ] @NaY, as tem-
slowly added diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,2-
phenylenediamine and 1,2-diaminocyclohexane, (under Ar atmosphere). The
mixture was heated under reflux condition for 24 h. The solution was filtered
and the resulting zeolites, were Soxhlet extracted with chloroform (for 4 h)
and then with ethanol (for 4 h) to remove excess unreacted products from
amine-aldehyde condensation and any copper(II) complexes adsorbed onto
the external surface of the zeolite crystallites. The resulting solids were dried
2
+
2
O
2
]
ions was detected. Furthermore, the
2
+
2 2
at 70 °C under vacuum for 12 h. The remaining [Cu(O O )] ions in zeolite
were removed by exchanging with aqueous 0.1 M NaCl solutions. The stability
of the encapsulated complex nanoparticles was checked after the reaction by
UV–vis and possible leaching of the complex was investigated by UV–vis in the
reaction solution after filtration of the zeolite. The amounts of Cu(II)
complexes encapsulated in zeolite matrix were determined by the elemental
analysis and by subtracting the amount of Cu(II) complex left in the solutions
after the synthesis of the materials as determined by UV–vis spectroscopy,
from the amount taken for the synthesis.
2
+
‘
2 2
‘[Cu(R[15]N O )] @NaY (R = Et, Pr, Ph, Ch)” were characterized
by several techniques: chemical analysis and spectroscopic meth-
ods (FT-IR, UV/vis, XRD, BET, DRS, XPS). The Cu(II) complex nano-
particles are proposed to exhibit tetrahedral geometry.
Acknowledgement
[
24] A. Bailey, D.E. Fenton, S.J. Kitchen, T.H. Lilley, M.G. Williams, P.A. Tasker, A.J.
Leonng, L.F. Lindoy, J. Chem. Soc. Dalton Trans. 2989 (1991).
Author is grateful to Council of University of Kashan for provid-
ing financial support to undertake this work.
[25] E. Tas, M. Aslanoglu, A. Kilic, O. Kaplan, H. Temel, J. Chem. Res-(S) 242 (April)
2006).
(
[
[
26] H. Temel, H. Hosgören, M. Boybay, Spectrosc. Lett. 34 (2001) 1.
27] S. Senapoti, K.K. Sarker, T.P. Mondal, C. Sinha, Transit. Met. Chem. 31 (2006)
2
93.
References
[
[
28] S. Ilhan, H. Temel, I. Yilmaz, M. Sekerci, J. Organomet. Chem. 692 (2007) 3855.
29] M.T. Kaczmarek, I. Pospıeszna-Markıewıcz, W. Radecka-Paryzek, J. Inclus.
Phenom. Macro. Chem. 49 (2004) 115.
30] F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, third ed.,
Interscience, New York, 1972.
31] A.A.A. Emara, Synth. React. Inorg. Met.-Org. Chem. 29 (1999) 87.
32] T.M. Salama, I.O. Ali, H.A. Gumaa, Micropor. Mesopor. Mater. 113 (2008) 90.
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34] Chemical composition (experimental found are given in parentheses), IR
stretching frequencies, conductive electrical, magnetic momentum, UV. Vis
and mass data of neat and zeolite-encapsulated copper(II) complex
[
[
[
1] P.K. Dutta, J. Inclus. Phenom. Mol. Recognit. Chem. 21 (1995) 215.
2] N.F. Curtis, Coordin. Chem. Rev. 3 (1968) 3.
3] P. Comba, N.F. Curtis, G.A. Lawrence, M.A. O’Leary, B.W. Skelton, A.H. White, J.
Chem. Soc. Dalton Trans. (1988) 2145.
[
[
[
[
[
[
4] N.F. Curtis, in: G.A. Melson (Ed.), Coordination Chemistry of Macrocyclic
Complexes, Plenum, New York, 1982, p. 219.
[
[
[
[
[
5] M. Salavati-Niasari, H. Najafian, Polyhedron 22 (2003) 2633.
6] M. Salavati-Niasari, F. Davar, Inorg. Chem. Commun. 9 (2006) 175.
7] M. Salavati-Niasari, Inorg. Chem. Commun. 7 (2004) 698.
8] M. Salavati-Niasari, J. Mol. Catal. A: Chem. 217 (2004) 87.
9] M.P. Suh, W. Shin, D. Kim, S. Kim, Inorg. Chem. 23 (1984) 618.
nanoparticles: Anal. Calc. for [Cu(Et[15]N
3
1
2
O
2
)](ClO
4
)
2
: C: 37.61 (37.46), H:
(DMF):
(Ar–CH): 3070,
(ClO4 ): 1110, 532, (Substituted
eff (B.M): 1.93, UV–vis (kmax, nm)
)](ClO }–
O–H] , 371,{[Cu(Et[15]N
)](ClO C: 38.69
.99 (3.86), N: 4.62 (4.75), C/N: 8.14 (7.89), Cu: 10.47 (10.23),
K
M
[
[
10] M.P. Suh, W. Shin, H. Kim, C.H. Koo, Inorg. Chem. 26 (1987) 1846.
11] J.B. Harrowfield, A.J. Herbit, P.A. Lay, A.M. Sargeson, A.M. Bond, J. Am. Chem.
Soc. 105 (1983) 5503.
ꢁ1
2
ꢁ1
ꢁ1
80
X
cm mol , IR data (KBr,
m
2
cm ): m(H O): 3334, m
ꢁ
m(Alph.–CH): 2940, 2873,
m(C@N): 1615,
m
m
benzene): 758,
m
(Cu–O): 460, m(Cu–N): 350, l
[
[
12] S.G. Kang, M.S. Kim, K. Ryu, Polyhedron 15 (1996) 1835.
13] M. Rossignoli, P.V. Bernhardt, G.A. Lawrance, M. Maeder, Aust. J. Chem. 50
(
DMF): 240, 271, 328, 611, Mass spectra: m/z: 570, {[Cu(Et[15]N
2
O
2
4 2
)
+
+
2
O
H
2
O–H] , 470, {[Cu(Et[15]N
2
O
2
)](ClO
4
)}–ClO
4
–2H
2
2
(
1997) 529.
+
2
)]}–2ClO
4
–2H
2
O–H] . Anal. Calc. for [Cu(Pr[16]N
2
O
2
4 2
) :
[
[
[
[
[
14] M. Salavati-Niasari, Inorg. Chem. Commun. 7 (2004) 963.
15] M. Salavati-Niasari, Chem. Lett. 34 (2005) 244.
16] M. Salavati-Niasari, F. Davar, Inorg. Chem. Commun. 9 (2006) 263.
17] R.W. Stotz, R.C. Stoufer, Chem. Commun. (1970) 1682.
(
38.52), H: 4.22 (4.17), N: 4.51 (4.69), C/N: 8.58 (8.21), Cu: 10.23 (10.11),
ꢁ1
2
ꢁ1
ꢁ1
K
3
M
(DMF): 175
X
cm mol , IR data (KBr,
m
cm ):
m
(H
2
O): 3340,
m
(Ar–CH):
ꢁ
052,
m
(Alph.–CH): 2941, 2872,
m
(C@N): 1613,
(Cu–O): 461, m(Cu–N): 355, leff (B.M): 1.95,
m
(ClO4 ): 1110, 532,
m(Substituted benzene): 758,
m
18] N. Herron, G.D. Stucky, C.A. Tolman, J. Chem. Soc., Chem. Commun. 1521
UV–vis (kmax, nm) (DMF): 240, 271, 328, 613, Mass spectra: m/z: 584,
(
1986).
+
{[Cu(Et[15]N
2
O
2
)](ClO
385,{[Cu(Et[15]N
)](ClO : C: 42.18 (42.03), H: 3.69 (3.54), N: 4.28 (4.38), C/
4
) }–2H
2
2
O–H] , 484, {[Cu(Et[15]N
2
O
2
)](ClO
4
)}–ClO
4
–
[
[
[
[
[
19] M. Salavati-Niasari, A. Sobhani, J. Mol. Catal. A: Chem. 285 (2008) 58.
20] M. Salavati-Niasari, Micropor. Mesopor. Mater. 92 (2006) 173.
21] M. Salavati-Niasari, F. Davar, M. Mazaheri, Mater. Lett. 62 (2008) 1890.
22] M. Salavati-Niasari, Micropor. Mesopor. Mater. 95 (2006) 248.
23] Preparation of [1,3-Bis(2-carboxyaldehydephenoxy)propane] (dialdehyde):
Dialdehyde was prepared by refluxing a mixture of 2-hydroxybenzaldehyde
+
+
2
H
2
O–H] ,
2 2 4 2
O )]}–2ClO –2H O–H] .
Anal. Calc.
for
[
Cu(Ph[15]N
2
O
2
4 2
)
ꢁ1
2
ꢁ1
N: 9.86 (9.59), Cu: 9.70 (9.53),
cm ):
K
M
(DMF): 170
(Alph.–CH): 2944,
(Substituted benzene): 758, (Cu–O): 468, m
X
cm mol , IR data (KBr,
(C@N): 1624,
(Cu–N): 361,
m
ꢁ1
m
(H
2
O): 3350,
m(Ar–CH): 3075,
m
m
ꢁ
m
ðClO Þ:1110, 532,
m
m
4
l
eff (B.M): 1.96, UV–vis (kmax, nm) (DMF): 240, 271, 328, 609, Mass spectra: m/
(
3
4.0 g, 30 mmol), 1,3-dibromopropane (1.5 ml, 15 mmol) and K
0 mmol) in dry acetone (30 ml). After the completion of the reaction (18 h),
2
CO
3
(4.1 g,
+
z: 618, {[Cu(Et[15]N
2
O
2
)](ClO
O–H] , 420,{[Cu(Et[15]N
Cu(Ch[15]N )](ClO : C: 41.80 (41.69), H: 4.57 (4.43), N: 4.24 (4.36), C/
4
2
) }–2H
2
O–H] , 519, {[Cu(Et[15]N
2
O
2
)](ClO
4
)}–
+
+
ClO
[
4
–2H
2
O )]}–2ClO –2H O–H] . Anal. Calc. for
2 2 4 2
the acetone was evaporated under vacuum and the resulting solid washed
with water to extract the formed KBr. The crude solid product was then
recrystallized
2
O
2
4 2
)
ꢁ1
2
ꢁ1
N: 9.86 (9.56), Cu: 9.61 (9.49),
cm ):
K
M
(DMF): 173
(Alph.–CH)
(Substituted benzene): 758, (Cu–O): 466, m
X
cm mol , IR data (KBr,
2876, (C@N): 1620,
(Cu–N): 354,
m
from
95%
ethanol
to
afford
pure
1,3-Bis(2-
ꢁ1
m
(H
2
O): 3342,
m(Ar–CH): 3066,
m
:
m
carboxyaldehydephenoxy)propane in 55% yield: m.p. 125–129 °C, IR (KBr)
ꢁ
ꢁ
1
1
m
ðClO
4
Þ:1110, 532,
m
m
t
4
6
1
1
(
max 2952, 1701, 1600, 1462, 1243 and 1158 cm
00 MHz) d 9.86 (s, 2H), 7.93 (d, 8.9 Hz, 4H), 7.23 (d, 8.8 Hz, 4H), 4.40 (t,
,
H
NMR (DMSO-d
6
,
l
eff (B.M): 1.99, UV–vis (kmax, nm) (DMF): 240, 271, 328, 610, Mass spectra: m/
+
1
3
z: 624, {[Cu(Et[15]N
2
O
2
)](ClO
O–H] , 425,{[Cu(Et[15]N
.50, Na: 3.28, Si/Al: 2.53, Surface area: 545 m /g, pore volumen: 0.31 ml/g,
Anal. Calc. for Cu(II)–NaY: Si: 21.53, Al: 8.53, Na: 3.36, Co: 3.71, Si/Al: 2.53,
4
)
2
}–2H
2
2
O–H] , 524, {[Cu(Et[15]N
2
O
2
)](ClO
4 2
–2H O–H] . NaY: Si: 21.48, Al:
2
4
)}–
.5 Hz, 4H) and 2.3 (quintet, 6.3 Hz, 2H), C NMR (DMSO-d
62.7, 131.2, 129.1, 114.6, 64.2 and 27.6.Preparation of [Cu(R[15 or
6]N )](ClO O (R = Et, Pr, Ph, Ch): To a stirred solution of dialdehyde
ꢀ2H
1.40 g, 5 mmol) and Cu(ClO O (1.85 g, 5 mmol) in MeOH (60 ml) was
6
, 80 MHz) d 190.5,
+
+
ClO
8
4
–2H
2
O
2
)]}–2ClO
O
2 2
4
)
2
2
4
)
2
ꢀ6H
2
2
2+
Surface area: 532 m /g, pore volumen: 0.30 ml/g, [Cu(Et[15]N
1
5
nm): 608, IR data (KBr,
11.12, H: 1.19, N: 1.33, Cu: 2.83, C/N: 8.36, Cu/N: 2.13, Si: 21.24, Al: 8.39, Na:
5
2
O
2
)] @NaY: C:
added dropwise various diamines (5 mmol) in MeOH (40 ml). After the
addition was completed, the stirring was continued for 2 h. Then the
precipitate was filtered and washed with MeOH and dried in air. The
0.80, H: 1.19, N: 1.36, Cu: 2.87, C/N: 7.94, Cu/N: 2.11, Si: 21.26, Al: 8.40, Na:
.35, Si/Al: 2.53, Surface area: 475 m /g, pore volumen: 0.18 ml/g, DRS (kmax,
2
ꢁ1
2+
2 2
m(C@N) cm ), 1612. [Cu(Pr[16]N O )] @NaY: C:
products
Cu(dialdehyde)] @NaY ([Cu(O
suspended in 100 ml distilled water, which contained Cu(ClO
were
crystallized
from
hot
methanol.Preparation
2 g NaY zeolite was
ꢀ6H
of
2
+
2+
[
2
O
2
)] @NaY):
A
2
.34, Si/Al: 2.53, Surface area: 473 m /g, pore volumen: 0.17 ml/g, DRS (kmax,
4
)
2
2
O

2
72
M. Salavati-Niasari / Inorganic Chemistry Communications 13 (2010) 266–272
nm): 610, IR data (KBr,
m
(C@N) cmꢁ1), 1610. [Cu(Ph[15]N
2
O
2
)]2+@NaY: C:
12.54, H: 1.35, N: 1.29, Cu: 2.82, C/N: 9.72, Cu/N: 2.18, Si: 21.22, Al: 8.39, Na:
2
1
2.60, H: 1.37, N: 1.30, Cu: 2.81, C/N: 9.69, Cu/N: 2.16, Si: 21.20, Al: 8.38, Na:
5.30, Si/Al: 2.53, Surface area: 457 m /g, pore volumen: 0.14 ml/g, DRS (kmax
,
2
ꢁ1
5
.29, Si/Al: 2.53, Surface area: 457 m /g, pore volumen: 0.14 ml/g, DRS (kmax
,
nm): 607, IR data (KBr,
m
(C@N) cm ), 1617.
ꢁ
1
2+
nm): 606, IR data (KBr,
2 2
m(C@N) cm ), 1620. [Cu(Ch[15]N O )] @NaY: C: