Palladium supported SBA-functionalizd 1,2-dicarboxylic acid: The first Pd-based heterogeneous synthesis of fluorenones

Article abstract of DOI:10.1016/j.mcat.2017.12.035

The first Pd-based heterogeneous homo- and cross-coupling reactions for the fluorenones synthesis are reported. The palladium supported SBA-functionalizd 1,2-dicarboxylic acid (Pd@DCA-SBA) was prepared and characterized by the FT-IR, TGA, AAS, TEM, and EDS measurements. The prepared catalyst exhibited a high performance in some homo and cross coupling reactions for the synthesis of fluorenone derivatives using 2-bromo or 2,7-dibromo fluorenone in ethanol-water as green solvent medium.

Full text of DOI:10.1016/j.mcat.2017.12.035

Molecular Catalysis 447 (2018) 28–36
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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
Palladium supported SBA-functionalizd 1,2-dicarboxylic acid:
The first Pd-based heterogeneous synthesis of fluorenones
Abolfazl Mohammadkhanni, Ayoob Bazgir∗
Department of Chemistry, Shahid Beheshti University, General Campus, Tehran, 1983963113, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
The first Pd-based heterogeneous homo- and cross-coupling reactions for the fluorenones synthesis are
reported. The palladium supported SBA-functionalizd 1,2-dicarboxylic acid (Pd@DCA-SBA) was prepared
and characterized by the FT-IR, TGA, AAS, TEM, and EDS measurements. The prepared catalyst exhibited a
high performance in some homo and cross coupling reactions for the synthesis of fluorenone derivatives
using 2-bromo or 2,7-dibromo fluorenone in ethanol-water as green solvent medium.
© 2017 Elsevier B.V. All rights reserved.
Received 14 October 2017
Received in revised form
19 December 2017
Accepted 24 December 2017
Available online 4 February 2018
Keywords:
Heterogeneous palladium catalyst
Fluorenone
2-Bromo fluorenone
Cross-coupling reaction
Homo-coupling reaction
1. Introduction
remain the most popular choice as support [9]. In fact, the reduc-
tion of the time and energy for achieving chemical transformations
These days, the green chemistry is one of the most important
research activities for chemists in both laboratory and industry.
Therefore, many efficient, eco-friendly and clean synthetic methods
have been developed for the synthesis of biologically and indus-
trially active molecules [1]. The heterogeneous catalyzed coupling
reactions in order to C C bond formation are a one of the substantial
areas of green chemistry research [2]. The metal-catalyzed coupling
reactions play an important role for the preparation of complex
molecules such as dyes, pharmaceuticals, natural products, func-
tional materials, agrochemicals and herbicides [3]. Palladium is a
widely applied metal for the wide range of coupling reactions and a
number of homogeneous catalytic systems like phosphines [4], pal-
ladacycle complexes [5], Schiff base ligands [6], and N-heterocyclic
carbenes [7] have been reported for this transformation. Eventually,
these homogeneous systems have several inherent limitations such
as high catalyst loading, catalyst separation and recycling, and con-
tamination of product with traces of heavy metals. Consequently,
various supported Pd catalysts with improved recycling and recov-
ery properties have been reported to overcome this drawbacks
[2,8]. Because of the good accessibility and porosity, mechanical
stability, relatively low cost, high thermal, and good catalytic per-
formance, SBA-15 and MCM-41 as mesoporous silica materials
and separations is the main aim of these attempts. Recently, inter-
est in palladium supported on SBA-based heterogeneous catalysts
in green media is dramatically increasing from a sustainable chem-
istry point of view [10].
Fluorenone as a polycyclic aromatic compounds find an ever
growing application in medicinal chemistry and photoelectric
material science (Fig. 1) [11]. The fluorenone moiety is found in nat-
ural biologically active compounds [12]. For example, dendroflorin
(I) is a natural product isolated from the Dendrobium densiflorum
and have a good performance in antioxidant activity [12][12b].
Tilorone (II), trade names Amixin, Lavomax, as interferon-inducer
is used as an antiviral drug and was found to possess potent
affinity for the agonist site of the ␣7 neuronal nicotinic recep-
tor [13]. The gold diethynylfluorene (III) was shown to possess a
significant cytotoxic activity on human cancer cells [14]. Polyflu-
orenes and oligofluorenes are very important candidates for blue
light-emitting materials [15]. Two aryl substituted fluorenone com-
pounds DPF (IV) and MDPF (V) as organic luminescence materials
was synthesized and exhibited prominent aggregation-induced
enhanced emission with high solid-state fluorescence quantum
yields [16]. Bisfluorenone (VI) has been synthesized as poten-
tial solute in liquid scintillation detector systems [17]. Therefore,
various methods have been reported for the preparation of flu-
orenones such as cyclization of 2-amino diaryl ketones [18] or
biaryl carboxylic acids [19], and oxidation of fluorenol [20]. One
of the most applicable methods for the synthesis of fluorenones
∗
Corresponding author.
E-mail address: a bazgir@sbu.ac.ir (A. Bazgir).
https://doi.org/10.1016/j.mcat.2017.12.035
2468-8231/© 2017 Elsevier B.V. All rights reserved.

A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
29
Fig. 1. Representatives of important fluorenones.
is the Pd-catalyzed coupling reactions. In 2016, the synthesis of
fluorenone derivatives has reported through Pd-catalyzed ortho-
selective oxidative C H/C H cross-coupling of aromatic carboxylic
acids with arenes and subsequent intramolecular Friedel-Crafts
acylation [21]. The synthesis of various substituted fluoren-9-ones
has been accomplished by the Pd-catalyzed cyclocarbonylation
of o-halobiaryls [22]. Some aryl fluorenones have been synthe-
sized as precursor for the synthesis of biologically and industrially
compounds via homogeneous Suzuki [11g,16,23] or Sonogashira
coupling reaction [24] using 2-bromo or 2,7 dibromo fluorenone.
Although there are several synthetic routes to make fluorenones
as mentioned above, to the best of our knowledge, employing
Pd-based heterogeneous catalyst for the synthesis of fluorenone
derivatives has not been previously reported. Herein, for the first
time an efficient and reusable heterogeneous catalyst for the syn-
thesis of fluorenones in green solvent medium (ethanol-water) [25]
has been reported.
The Pd@DCA-SBA nanocomposite was characterized by FT-IR,
TGA, AAS, TEM, and EDS measurements. The FT-IR spectrum of SBA-
DCA and Pd@DCA-SBA are shown in Fig. 2. The FT-IR spectrum of
SBA-DCA shows a characteristic band at 1656 cm−1 ascribe to C
O
of carboxylic acid groups. This clearly confirms the functionaliza-
tion of SBA by 1,2-bidentate carboxyl groups. The C O bands of
Pd@DCA-SBA were shifted to a lower frequency in the IR spectrum
(1627 cm−1) due to the formation of a metal–ligand bond [27].
Thermogravimetric analysis (TGA) was further used to study the
composition of the Pd@DCA-SBA nanocomposite (Fig. 3). TGA plot
of catalyst shows a weight loss at ∼100 ◦C and was assigned to
adsorbed water. The 8.3% weight loss at above ∼220 ◦C (and con-
tinuing to ∼600 ◦C) is related to the decomposition of covalently
bonded organic groups from the Pd@DCA-SBA. It shows that the
catalyst has good thermal stability until 220 ◦C. The palladium con-
tent of Pd@DCA-SBA nanocomposite was calculated (0.5 mmol g−1
by AAS.
)
The morphology of fresh SBA-15 and Pd@DCA-SBA nanocom-
posite were determined by transmission electron microscopy
(TEM). The Fig. 4a shows the porous structure of fresh SBA-15. A
good distribution of palladium nanoparticles with average particle
size of 12–15 nm is illustrated in Fig. 4b,c and indicates no change in
the porous structure of the support and also no detectable aggrega-
tion of Pd nanoparticles. The energy dispersive X-ray spectroscopy
(EDS) of Pd@DCA-SBA nanocomposite also clearly shows the pres-
ence of elements Pd, C, O and S in the composite (Fig. 5).
2. Results and discussion
2.1. Synthesis and characterization of Pd@DCA-SBA
nanocomposite
The preparation process for the palladium supported SBA-
functionalizd 1,2-dicarboxylic acid (Pd@DCA-SBA) nanocomposite
is shown in Scheme 1. The SBA-Cl obtained by the reaction of
SBA-15 with thionyl chloride. Then, SBA-Cl was reacted with 2-
mercaptoethanol to obtain mercaptofunctionalized SBA (SBA-SH)
[26]. Subsequently, the reaction of SBA-SH with maleic anhydride
followed by hydrolysis leads to the SBA supported 1,2-dicarboxylic
groups (SBA-DCA). The final catalyst (Pd@DCA-SBA nanocompos-
ite) was prepared by the reaction of SBA-DCA with an acetonitril
solution of palladium acetate at room temperature.
2.2. The catalytic activity of the catalyst
For fluorenones synthesis, the catalytic activity of Pd@DCA-SBA
nanocomposite was investigated in the Suzuki-Miyaura cross cou-
pling reaction of 2-bromo fluorenone 1 and aryl bronic acids 2. The

30
A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
Scheme 1. The schematic diagram of catalyst preparation.
Fig. 2. FT-IR spectra of SBA-DCA (A) and Pd@DCA-SBA (B).
Fig. 3. TGA of Pd@DCA-SBA nanocomposite.
coupling reaction of 2-bromo fluorenone 1a and phenyl boronic
acid 2a was chosen as model reaction in different conditions. By
using K2CO3 as base and in the presence of 0.2 mol% catalyst, the
reaction was tested employing various solvents such as H2O, MeOH,
EtOH, H2O-EtOH, and toluene at 80 ◦C (Table 1, entries 1–5). A
superior yield was obtained when H2O-EtOH (1:1) was used as

A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
31
Fig. 4. TEM image of fresh SBA-15 (A) and Pd@DCA-SBA nanocomposite (B, C).
Fig. 5. Energy dispersive X-ray spectroscopy (EDS) of Pd@DCA-SBA.
the solvent (Table, Entry 5). Then, different bases were screened
in the model reaction. The reaction did not proceed in the pres-
ence of NaHCO3 and moderate yield was obtained with Cs2CO3 and
KOtBu (Table 1, Entry 6–8). Also, some experiments were carried
out in different temperature and 80 ◦C was the optimum reaction
temperature (Table 1, Entries 5, 9 and 10). The effect of amount
of Pd@DCA-SBA was also investigated under the optimum reac-
tion conditions (Entries 5, 11 and 12). It was found that when the
amount of catalyst increased from 0.1 and 0.2 to 0.3 mol%, the yield
increased from 71% and 85%, and 86%, respectively. It was found
that 0.2 mol% Pd@DCA-SBA is sufficient to push this reaction for-
ward (Table 1, entry 5). Then, the effect of dicarboxylic acid groups
in the catalyst was investigated. The palladium supported on SBA-
15 as an unmodified SBA-15 catalyst was synthesized and tested in
the model reaction in optimum reaction conditions. As can be seen
in Table 1, the yield of product was 62% (Entry 13). According to the

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A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
Scheme 2. Synthesis of 2,7-diaryl fluorenones.
Table 1
result, the dicarboxylic acid groups make higher catalytic activity
for the reaction.
Screening of the reaction conditionsa.
After optimization of the reaction conditions, we screened vari-
ous boronic acids to explore the scope of the reaction (Table 2). The
catalyst showed good reactivity and the reaction was performed
with good to excellent yield with boronic acids containing both
electron donating and electron withdrawing functionalities.
The catalyst was even effective for synthesis of 2,7-diaryl
fluorenones 4 by Suzuki reaction of two sites of 2,7-dibromo
fluorenones 1b with boronic acids 2 using 0.3 mol% catalyst
(Scheme 2). The compound 5 has been synthesized via homoge-
neous Pd-catalyst and reported as potential material in organic
electroluminescence systems [30]. As shown in Scheme 2, the cat-
alyst was successfully applied to prepare compound 5 through a
Suzuki cross-coupling and subsequently Knoevenagel condensa-
tion with malononitrile.
Encouraged by this success, we examined the catalytic activity of
Pd@DCA-SBA nanocomposite in Ullmann homocoupling reaction of
2-bromo fluorenone 1a in the presence of 0.2 mol% of catalyst. After
optimization of reaction conditions, the 9H,9ꢀH-[2,2ꢀ-bifluorene]-
9,9ꢀ-dione 6 was obtained in 60% yield in the presence of glucose
as a reducing agent [31] (Scheme 3).
Entry
Solvent
Catalyst (mol%)
Base
T (◦C)
Yieldb (%)
1
2
3
4
5
6
7
8
H2O
EtOH
MeOH
Toluene
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
H2O-EtOH (1:1)
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.3
10.
0.2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
KOtBu
Cs2CO3
NaHCO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
80
80
80
80
80
80
80
80
60
90
80
80
80
52
65
32
48
85
64
75
<20
71
83
86
71
62
9
10
11
12
13c
a
phenylboronic acids (1.2 mmol), 2-bromo fluorenone (1 mmol), base (2 mmol).
Isolated yield.
Catalyst = Pd@SBA.
b
c
Table 2
Synthesis of fluorenones by the Suzuki reaction.
Product 3
X
Y
Time (h)
Yield (%)a
M.P. (◦C)
Ref.
a
b
c
d
e
f
H
H
H
H
Br
Br
H
1.5
2
2
1.5
3
2
85
83
84
85
84
85
141–142
138–139
140–142
177–178
209–211
211–212
[28]
[23a]
[29]
–
[23c]
–
OMe
Me
CF3
H
OMe
aIsolated Yield.

A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
33
Fig. 6. The UV/Vis spectra of selected compounds.
Scheme 3. Synthesis of 9H,9ꢀH-[2,2ꢀ-bifluorene]-9,9ꢀ-dione 6.
Scheme 4. The Hiyama cross-coupling reaction for the synthesis of 2-phenyl fluorenone 3a.
Table 3
observed that the products are fluorescent in solution and their ␭
flu
Photophysical data for absorption (abs) and fluorescence (flu) of selected products
in CHCl3.
are at green light (560–570 nm). The ␭ are presented in Table 3.
flu
The observation of great potential activity of the catalyst in
Suzuki coupling reaction of aryl boronic acids and bromo fluo-
renones encouraged us to investigate the activity of catalyst in
Suzuki reaction for biaryl synthesis. As can be seen from Table 4, the
Suzuki coupling of aryl iodides and bromides 8 with aryl boronic
acids 2 in the presence of 0.2 mol% of the catalyst using K2CO3 as a
base in H2O-EtOH at 80 ◦C afforded biaryl derivatives 9 in excel-
lent yields. Under the same reaction conditions the coupling of
chlorobenzene provided the target product in good yields.
-
Compound
log C
␭
abs,max/nm
␭flu,max/nm
3b
3d
4a
4b
6
3.26
3.28
3.21
3.30
3.17
306
203
296
302
296
570
560
570
560
570
The catalyst was even effective for the synthesis of teiphenyl 11
by the reaction of 2,4-diIodo benzene 10 including two sites with
boronic acids 2 (Scheme 5).
To the best of our knowledge, synthesis of fluorenone deriva-
tives via Hiyama cross-coupling reaction has not been previously
reported. Therefore, the application of the Pd@DCA-SBA catalyst in
Hiyama cross-coupling reaction of triethoxy(phenyl)silane 7 and
2-bromo fluorenone 1a was tested at the same reaction conditions
(0.2 mol% cat., K2CO3) and corresponding product 3a was obtained
in 42% yield after 4 h. It was found that increasing amounts of the
catalyst and reaction time did not improve the yield. A review to the
literatures revealed us that NaOH is good choice as the base [32].
Consequently, we checked the reaction in H2O-EtOH using NaOH
in the presence of 0.2 mol% of catalyst and product 3a was obtained
in 65% yield (Scheme 4).
Then, we examined the heterogeneous nature of the catalyst.
First, we performed a mercury poisoning test by entering an excess
amount of Hg in the Suzuki reaction of phenylboronic acid and 2-
bromo fluorenone 1a. The reaction yield fell down in the presence
of mercury due to the amalgamation with PdNPs. The results con-
firm us the heterogeneous nature of the catalyst, more over it can be
concluded that Suzuki reaction proceeded via Pd(0)/Pd(+2) mech-
anism [33]. In the next step, to assess the palladium leaching from
the catalyst during the reaction we performed the hot filtration test
for Suzuki reaction of 2-bromo fluorenone 1a and phenylboronic
acid. The reaction was stopped after ∼50% of the reaction. The hot
filtrates were then transferred to another flask containing base and
H2O-EtOH at 80 ◦C. Upon further heating of the catalyst-free solu-
tion for 7 h, no considerable progress (∼6% by GC analysis) was
observed. Moreover, using AAS of the same reaction solution at the
Electronic absorption and fluorescence spectra of 2 × 10−5 M
solutions of selected products 3, 4 and 6 in CHCl3 were mea-
sured and the results are shown in Table 3 and Figs. 6 and 7. All
selected compounds showed strong absorptions, with maximum
wavelengths in the range of 296–306 nm (Fig. 6). Fig. 7 shows
the emission spectra of selected products. From Fig. 7, it can be

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A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
Fig. 7. The fluorescence spectra of selected compounds.
Scheme 5. Suzuki reaction of aryl boronic acids with 2,4-diiodo benzene.
Table 4
3. Experimental
Suzuki reaction for the biaryl synthesis.
3.1. Preparation of SBA-Cl [26]
Thionyl chloride (8 mL) was added to 1 g of oven dried SBA-15
(120 ◦C, vacuum) in a round bottomed flask equipped with a con-
denser and a drying tube and refluxed for 48 h. Excess of thionyl
chloride was distilled off and the resulting product was flame-dried
and stored in a sealed vessel. This silica chloride can be used for
months without losing its activity.
Product 5
Y
X
R
Time (h)
Yield (%)
a
b
c
d
e
f
g
h
i
H
H
H
I
I
I
I
I
I
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
H
2
2
2
2
4
2
2
2
2
2
2
8
8
8
8
95
94
95
95
95
94
95
92
93
95
94
78
80
79
76
4-Me
4-OMe
H
4-COMe
2-Me
H
4-NO2
4-NO2
4-Me
4-Me
4-NO2
4-NO2
H
3.2. Preparation of SBA-SH
4-OMe
H
H
H
2-Mercaptoethanol (3 mL) was added to 1 g SBA-Cl and was
stirred vigorously for 24 h at room temperature. Then the mixture
was filtered and washed with ethanol, acetone, and water.
H
4-OMe
H
4-Me
H
4-OMe
4-Me
H
j
3.3. Preparation of SBA-DCA [27]
K
M
N
O
P
SBA-15–SH (2.0 g) and maleic anhydride (1.96 g, 20 mmol) in
50 mL of THF was stirred at room temperature under argon atmo-
sphere. After 1 h, triethylamine (5 mmol) was added and stirred for
24 h. The products were collected by centrifugation and washed
with water. Then, the product was stirred in deionized water at
80 ◦C for 24 h for dicarboxyl groups formation. Finally, the products
were washed with water, ethanol and acetone and dried.
H
aIsolated yield.
midpoint of completion indicated that no significant quantities of
palladium are lost to the reaction liquors during the process. The
reusability of the catalyst was also investigated in the Suzuki cou-
pling reaction of phenylboronic acid with three haloarenes, phenyl
iodide, 2-bromo fluorenone and phenyl chloride. As can be seen in
Fig. 8, the catalyst could be reused successively at least five times
without significant loss of activity. All results confirm the reaction
occurs mainly via a heterogeneous pathway. In addition, as shown
in Fig. 9, no detectable aggregation for palladium NPs was observed
in the recovered Pd@DCA-SBA nanocomposite after 5 runs.
3.4. Preparation of Pd@DCA-SBA nanocomposite
The SBA-DCA (0.5 g) was ultrasonically dispersed in 5 mL of
deionized water. Then, a solution of Pd(OAc)2 (0.2 g) in acetonitrile
was added and the mixture was stirred for 10 h. After filtration and
washing with deionized water, acetonitrile and ethanol the final
material was dried at 70 ◦C for 12 h. The Pd concentration in the
Pd@DCA-SBA was determined by atomic adsorption spectroscopy

A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
35
Fig. 8. The reusability of the catalyst in the Suzuki reaction of phenylboronic acid with phenyl iodide, 2-bromo fluorenone and phenyl chloride.
Fig. 9. TEM image of Pd@DCA-SBA nanocomposite after 5 reaction cycles.
(AAS) following digestion with concentrated aqua regia solution at
80 ◦C, and was found to be 0.5 mmol g−1
reaction, the catalyst was separated and the filtrate was extracted
with ethyl acetate (2 × 5 mL). The organic solvents were removed
under vacuum and the product 3 was purified by preparative TLC
(n-Hexane).
3.5. General procedure for Suzuki reaction of 9-fluorenone
A mixture of Pd@DCA −SBA (0.2 mol% of Pd), K2CO3 (2 mmol),
9-fluorenone (1.0 mmol), aryl boronic acid (1.2 mmol) in H2O-EtOH
(3 mL, 1:1) was stirred at 80 ◦C for appropriate time (Table 2). After
completion of the reaction, the catalyst was separated and the
filtrate was extracted with ethyl acetate (2 × 5 mL). The organic sol-
vents were removed under vacuum and the product 3 was purified
by recrystalization.
3.8. General procedure for the Biaryl synthesis via Suzuki reaction
A mixture of Pd@DCA-SBA (0.2 mol% of Pd), K2CO3 (2 mmol),
aryl halide (1.0 mmol), and aryl boronic acid (1.2 mmol) in H2O-
EtOH (3 mL, 1:1) was stirred at 80 ◦C for appropriate time (Table 3).
After completion of the reaction, the catalyst was separated and the
filtrate was extracted with ethyl acetate (2 × 5 mL). The organic sol-
vents were removed under vacuum and the product 9 was purified
by preparative TLC (n-Hexane).
3.6. General procedure for the synthesis of bisfluorenone
A mixture of Pd@DCA-SBA (0.2 mol% of Pd), K2CO3 (2 mmol), 9-
fluorenone (1.0 mmol), glucose (1 mmol) in H2O-EtOH (3 mL, 1:1)
was stirred at 80 ◦C for 12 h at 80 ◦C. After completion of the reac-
tion, the catalyst was separated and the filtrate was extracted with
ethyl acetate (2 × 5 mL). The organic solvents were removed under
vacuum and the product 3 was purified by preparative TLC (n-
Hexane).
4. Conclusions
We have demonstrated for the first time that Pd@DCA-SBA
nanocomposite is an effective and powerful heterogeneous cata-
lyst for the synthesis of fluorenone derivatives by homo and cross
coupling reactions in H2O-EtOH as green solvent. In addition, the
negligible leaching of palladium from catalyst was proved by AAs
and the catalyst was recovered by simple filtration and reused for
several cycles without a significant loss of catalytic activity. Fur-
thermore, the TEM image of the recovered catalyst showed the
presence of well-distributed Pd NPs on the catalyst without any
aggregation. Further applications of the catalytic system in other
3.7. General procedure for the Hiyama reaction of 9-fluorenone
A mixture of Pd@DCA-SBA (0.2 mol% of Pd), NaOH (2 mmol), 9-
fluorenone (1.0 mmol), triethoxyphenylsilane (1.0 mmol), in H2O-
EtOH (3 mL, 1:1) was stirred at 80 ◦C for 4 h. After completion of the

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A. Mohammadkhanni, A. Bazgir / Molecular Catalysis 447 (2018) 28–36
palladium catalyzed reactions are under investigation in our labo-
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Acknowledgments
We gratefully acknowledge the financials Research Council of
Shahid Beheshti University.
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