Preparation, characterization, and theoretical study of nanoparticles of triphenylphosphonium tetrachloroaluminate(III) [P(C6H 5)3H]+[AlCl4]-

Article abstract of DOI:10.1080/15533174.2012.740737

Triphenylphosphonium tetrachloroaluminate(III) [P(C₆H ₅)₃H]⁺[AlCl₄]^-, TPPTCA, nanoparticle was synthesized by using triphenylphosphonium chloride addition to AlCl₃ in the presence of surfactant. The product was characterized by spectroscopic and analytical methods such as ³¹P-NMR, FT-IR, XRD, SEM, and CHN. Theoretical calculations were used for the structural optimization of this compound. The structure of compound has been calculated and optimized by the density functional theory (DFT) based method at B3LYP/6-311G levels of theory, using the Gaussian 03 package of programs. The comparison between theory and experiment is made. On the base of the application of scanning electron microscopy is showed about 54 nm particle sizes. Copyright Taylor & Francis Group, LLC.

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Preparation, Characterization, and Theoretical
Study of Nanoparticles of Triphenylphosphonium
Tetrachloroaluminate(III) [P(C6H5)3H]+[AlCl4]-
Shahriar Ghammamy a
a Department of Chemistry, Faculty of Science , Imam Khomeini International University ,
Qazvin , I. R. Iran
Accepted author version posted online: 04 Dec 2012.Published online: 26 Feb 2013.
To cite this article: Shahriar Ghammamy (2013) Preparation, Characterization, and Theoretical Study of Nanoparticles of
Triphenylphosphonium Tetrachloroaluminate(III) [P(C6H5)3H]+[AlCl4]- , Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, 43:4, 390-394, DOI: 10.1080/15533174.2012.740737
To link to this article: http://dx.doi.org/10.1080/15533174.2012.740737
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:390–394, 2013
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2012.740737
Preparation, Characterization, and Theoretical Study
of Nanoparticles of Triphenylphosphonium
Tetrachloroaluminate(III) [P(C6H5)3H]+[AlCl4]−
Shahriar Ghammamy
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin,
I. R. Iran
(amplifiers, switches, ion hosts) made from fine-grained ce-
ramic nanomaterials produced by the low-temperature sinter-
ing of high-purity nanoparticles and powders can be produced
at a relatively low cost. These components are free of inter-
nal stress or intrinsic birefringence, and allow relatively large
doping levels or optimized custom designed doping profiles.
This highlights the use of ceramic nanomaterials as being
particularly important for high-energy laser elements and ap-
plications. A new class of alumina compounds, specifically
nanoparticles and nanocompounds, was investigated. Another
side the phosphorus chemistry has been developed in two re-
cent years as one of the most important branches of science.[1]
Many biological processes such as energy transfer, bone syn-
thesis, amino acid synthesis, and metabolism require phospho-
rus and phosphate esters.[2,3] For the hydrolysis of RNA and
phospholipids, cyclic phosphate esters are of biological signifi-
cance.[4] In recent years[5–11] have synthesized a series of alumi-
nates using the sonochemical method, but in the present work,
[P(C6H5)3H]+[AlCl4]− nanoparticles was synthesized by a sim-
ple method with the starting materials P(C6H5)3, HCl, AlCl3,
and a surfactant trimercaptopropionic acid (MPA), respectively.
In addition to the spectroscopic techniques such as 31P-NMR,
FT-IR, powder X-ray diffraction (XRD), and scanning electron
microscopy (SEM) theoretical calculations were used for this
compound by using B3LYP method with the 6–311G∗ basis set.
The molecular geometry and vibrational frequencies, energies,
molecular orbitals, and ground state were calculated.
Triphenylphosphonium tetrachloroaluminate(III) [P(C6H5)3
H]+[AlCl4]−, TPPTCA, nanoparticle was synthesized by using
triphenylphosphonium chloride addition to AlCl3 in the presence
of surfactant. The product was characterized by spectroscopic and
analytical methods such as 31P-NMR, FT-IR, XRD, SEM, and
CHN. Theoretical calculations were used for the structural op-
timization of this compound. The structure of compound has been
calculated and optimized by the density functional theory (DFT)
based method at B3LYP/6–311G levels of theory, using the Gaus-
sian 03 package of programs. The comparison between theory and
experiment is made. On the base of the application of scanning
electron microscopy is showed about 54 nm particle sizes.
Keywords characterization, nanoparticles, [P(C6H5)3H]+[AlCl4]−,
preparation, X-ray diffraction
INTRODUCTION
Transparent ceramics have recently acquired a high degree
of interest and notoriety. Basic applications include lasers and
cutting tools, transparent armor windows, night vision devices
(NVD), and nose cones for heat seeking missiles. Currently
available infrared (IR) transparent materials typically exhibit a
trade-off between optical performance and mechanical strength.
For example, sapphire (crystalline alumina) is very strong,
but lacks full transparency throughout the 3–5 μm mid-IR
range. Yttria is fully transparent from 3–5 μm, but lacks suffi-
cient strength, hardness, and thermal shock resistance for high-
performance aerospace applications. Not surprisingly, a combi-
nation of these two materials in the form of the yttria-alumina
garnet (YAG) has proven to be one of the top performers in
the field. It has been shown fairly recently that laser elements
EXPERIMENTAL
Materials and Instruments
Triphenylphosphine, hydrogen chloride (hydrochloric acid),
aluminum trichloride, trimercaptopropionic acid, and other all
materials were prepared from Merck Company (Darmstadt,
Tehran agent, Germany) and used as received without further
treatment. Solvents that were used for reactions purified and
dried by standard procedures. Infrared spectra were recorded
as KBr disks on a Bruker Tensor model 420 spectrophotometer
(Qazuin, IKI University, Iran). XRD diffractions were stud-
ied with X-ray diffraction device Siemens D500 Diffractometer
Received 25 January 2012; accepted 13 October 2012.
The authors wish to express their warm thanks to Dr. Gh.
RezaeiBehbahani for his valuable discussions. This work was sup-
ported by Islamic Azad University, Takestan Branch.
Address correspondence to Shahriar Ghammamy, Department of
Chemistry, Faculty of Science, Imam Khomeini International Univer-
sity, Qazvin, I. R. Iran. E-mail: shghamami@yahoo.com
390

NANORIPHENYLPHOSPHONIUM TETRACHLOROALUMINATE
391
model (Tehran University, Iran). In all phases of Cu-Kα radi-
ation with a wavelength of 1.5404 Å was used. The morpho-
logical studies by SEM were performed. NMR spectra were
recorded on a Bruker AVANCE DRX 500 spectrometer (Tarbiat
Modares University, Iran). All the chemical shifts are quoted in
ppm using the high frequency positive convention. The percent
composition of elements was obtained from the Microanalytical
Laboratories, Department of Chemistry, OIRC, Tehran (Iran).
Preparation of Triphenylphosphonium Chloride (TPPCl)
To a 500 mL flask equipped with a magnetic stirrer was
added hydrogen chloride (100 mmol) and triphenylphosphine
(100 mmol, 26.2 g) at 40–50◦C. The reaction mixture was stirred
for 20 min, cooled to room temperature, and filtered. The filtered
solid was washed with ether (2 × 50 ml), crystallized, and
identified.
FIG. 1. IR spectrum of [P(C6H5)3H]+[AlCl4]− (color figure available online).
mixing with RCl (R denotes such as an alkali metal or organic
cation), which is believed to originate from the Lewis acid–base
interactions of AlCl3 with RCl and the formation of large-sized
complex anions, such as AlCl4−, Al2Cl7−, and Al3Cl10−. From
the binary phase diagram, it is found that a low-lying eutectic oc-
curs in the 2:1 composition of AlCl3–RCl. Melting temperature
of the eutectic is well below that of the AlCl3, representing the
minimum liquid us temperature throughout the entire system.
In this letter, we report the synthesis, spectroscopic charac-
terization, and density functional theory calculations of a com-
pound by using B3LYP method with the 6–311G∗ basis set.
The molecular geometry and vibrational frequencies, energies,
and molecular orbitals are calculated by using the B3LYP at
6–311G∗ method.
Synthesis of Triphenylphosphonium
Tetrachloroaluminate(III), P(C6H5)3H]+[AlCl4]−
Triphenylphosphonium tetrachloroaluminate (III), P(C6H5)3
H]+[AlCl4]− was prepared by two methods. First, to aluminum
trichloride (0.6 g, 4.48 mmol) in acetonitrile (200 mL) was
added at room temperature a solution of triphenylphosphonium
chloride (1.33 g, 4.48 mmol) in acetonitrile (100 mL). Trimer-
captopropionic acid in excess amount (2.06 g) was added as
surfactant. After 50 min, a white precipitate formed, and diethyl
ether (100 mL) was added to the mixture, cooled, and filtered.
The solid product was washed with ether and hexane. Second,
triphenylphosphine (0.6 g, 2.28 mmol) was dissolved in ace-
tonitrile (10 mL) and stirred for 0.5 h. (0.08 g, 2.18 mmol) HCl
(37%) was added to this mixture and stirring continued for 5 min.
Trimercaptopropionic acid (MPA; 0.72 g) was added to the ma-
terials and stirring continued for another 5 min. AlCl3 (0.3 g,
2.24 mmol) in acetonitrile added to this mixture as the last of
starting materials and stirring was continued for 4 h to precipitate
a white solid. Precipitate was filtered and washed with ether and
hexane. M.P.: 83–84◦; Anal. Calcd. for P(C6H5)3H]+[AlCl4]−:
C, 50.03; H, 3.73. Found: C, 50.97; H, 3.82. IR (KBr) (cm−1):
Triphenylphosphonium trichloroaluminate (TPPTCA) can
be easily obtained by the addition of triphenylphosphonium
chloride to an acetonitrile solution of aluminum trichloride. The
3412, 1636, 1477, 1437, 973, 613 cm−1 31P NMR (135 MHz,
.
CDCl3): δ = 31.42 ppm (Figures 1 and 2).
RESULTS AND DISCUSSION
Preparation
The salt/Lewis acid adducts usually result in either ionic
liquids or crystalline materials with low melting points. Salts
containing large organic cations, such as butylpyridinium chlo-
ride or 1,3-dialkylimidazolium chloride, and interact with AlCl3
to form ionically conducting liquids at room temperature.[12–15]
Solid AlCl3 has a melting temperature at 193◦C. Upon melting,
AlCl3 consists primarily of discrete Al2Cl6 dimers, and ap-
pears as a molecular liquid with high vapor pressure. It is well
known[16] that the melting point of AlCl3 can be lowered upon
FIG. 2. 31P-NMR Spectrum of [P(C6H5)3H]+[AlCl4]−.

392
S. GHAMMAMY
FIG. 3. Optimized structure of [AlCl4]− anion (color figure available online).
FIG. 5. XRD pattern of [P(C6H5)3H]+[AlCl4]− (color figure available online).
advantages of the new method are the following: (a) there is no
side product, (b) the reaction is quite fast, (c) mild conditions,
and (d) the accompanied color change, which provides visual
means for ascertaining the progress of reaction.
This paper describes some initial work on the characteri-
zation of nanoparticles investigated the processing of prepara-
tion a novel nanoparticle with formula [P(C6H5)3H]+[AlCl4]−.
This goal was reached by reacting triphenylphosphonium chlo-
ride added to acetonitrile and AlCl3 Then trimercaptopropi-
onic acid was added to the starter materials. Reporting the
synthesis of the TPPTCA shows that aluminate was useful for
organic chemists, that is, the analog of the previous aluminate
compounds.
The reported methods for their preparation involved non-mild
or hard conditions such as high temperatures.
P(C6H5)3 + HCl + AlCl3 −→ [P(C6H5)3H]+[AlCl4]−
FIG. 4. Optimized structure of [P(C6H5)3H]+ cation (color figure available online).

NANORIPHENYLPHOSPHONIUM TETRACHLOROALUMINATE
393
FIG. 6. SEM graphs of nano [P(C6H5)3H]+[AlCl4]−.

394
S. GHAMMAMY
TABLE 1
croscopy. The spatial resolution of the SEM depends on the
Calculated and experimental frequencies of
size of the electron spot, which in turn depends on both the
wavelength of the electrons and the electron-optical system that
produces the scanning beam. The resolution is also limited by
the size of the interaction volume, or the extent to which the
material interacts with the electron beam. SEM pictures shows
agglomeration of particles and multiform of texture. SEM shows
the size of nanoparticles about 54 nm that confirm the predicted
size range by XRD (Figure 6).
[P(C6H5)3H]+[AlCl4]− (cm−1
)
[P(C6H5)3H]+[AlCl4]−
B3LYP/6311G
Expt.
υP(C6H5)
υC6H6
1485
1650
3433
1467
1000
620
1477
1638
3412
1437
973
υ
= C-H(str)
υ c c
υAl-Cl
υAl-Cl
CONCLUSIONS
In this work, a novel aluminate compound with formula
[P(C6H5)3H]+[AlCl4]− was synthesized from the reaction of
triphenylphosphonium with acetonitrile. The 31PNMR spectrum
of this compound indicates a signal at 31.42 ppm. The structure
of compound has been calculated and optimized by the den-
sity functional theory (DFT) based method at B3LYP/6-311G
levels of theory, using the Gaussian 03 package of programs.
The comparison between theory and experiment is made. This
compound was characterized by IR, XRD, and SEM techniques
(Figures 1–6). The nanoform of this compound was synthesized
and measured by FTIR, XRD, and SEM.
613
Ab Initio Calculations Method
All ab initio calculations were done by using the Gaussian-
98 suite of programs.[17] The cations and anions are commonly
assumed to be in a hypothetical gaseous free state and without
any pre-assumed symmetry, but some calculations also involve
better approximations to real systems. After the optimization
procedures, giving geometry with a minimum energy, perhaps
not a global one, the vibrational frequencies and intensities and
the eigenvectors for the normal modes are calculated and dis-
played on a computer screen, to identify the dominating motions.
Then the frequencies (wave numbers) have to be correlated with
the results of the IR experiments. The calculated and experi-
mental vibrational spectra are in more or less good agreement
(Table 1). The wave number (frequency) scale is often calcu-
lated as slightly too high, due to the lack of good modeling of the
orbitals and interactions with the surroundings. The structures
of the optimized [P(C6H5)3H]+[AlCl4]− in this product are de-
picted in (Figures 3 and 4) The Al atom in anion is coordinated
by four Cl atoms as ligands in tetrahedral geometry.
REFERENCES
1. Sengupta, S.K.; Pandey, O.P.; Rao, G.P.; Vishen, P. Metal Based Drugs
2002, 8, 293.
2. Suarez, P.; Dullius, J.E. L.; Einloft, S.; De Souza, R.R.; Dupont, J. Inorg.
Chim. Acta. 1997, 255, 207–209.
3. Boon, J.A.; Levisky, J.L.; Pflug, L.; Wilkes, J.S. J. Irg. Chem. 1986, 51,
480–483.
4. Yanes, E.G.; Gratz, S.R.; Baldwin, M.J.; Robinson, S.E.; Stalcup, A.M.
Anal. Chem. 2001, 73, 3838.
5. Lv, W.Z.; Luo, Z.K.; Yang, H. Ultrason. Sonochem. 2010, 17, 344.
6. Lv, W.Z.; Liu, B.; Qiu, Q. J. Alloys Compd. 2009, 479, 480.
7. Lv, W.Z.; Liu, B.; Luo, Z.K. J. Alloys Compd. 2008, 465, 261.
8. Lv, W.Z.; Luo, Z.K.; Liu, B. Key Eng. Mater. 2008,368, 604.
9. Lv, W.Z.; Liu, B.; Luo, Z.K. J. Mater. Sci. Eng. 2007, 25, 686.
10. Lv, W.Z.; Luo, Z.K.; Zhang, P.X. Inorg. Chem. Ind. 2007, 39, 16.
11. Lv, W.Z.; Liu, B.; Wei, S.H. J. Shenzhen Univ. 2006, 23, 329.
12. Cooper, E.I.; Sullivan, E.J. M. Proceedings of the 8th International Sympo-
sium on Molten Salts, 1992, 92–16, 386.
XRD and SEM Data
XRD of TPPTCA shown in Figure 5. The particle size can
be calculated. The size of the nano particles can be calculated
from the Scherrer equation used for this purpose.
13. Chum, H.L.; Koch, V.R.; Miller, L.L.; Osteryoung, R.A. J. Am. Chem. Soc.
1975, 97, 264–267.
D = 0.9 λ/B Cosθ
14. Wilkes, J.S.; Levisky, J.A.; Wilson, R.A.; Hussey, C.L. Inorg. Chem. 1982,
21, 1263–1264.
15. Lee, Y.; Price, D.L.; Curtiss, L.A.; Ratner, M.A.; Shriver, D.F. J. Chem.
Phys. 2001, 114, 4591–4594.
In the previous equation D is particle diameter (Å), B is the
width of the strongest peak at half height in radians, and θ
is the angle at which the peak appears. XRD analysis shows
that TPPTCA has nanosize about 50 nm and produced in
nanoscale.
Currently, the fastest and most routine method of determining
particle size is by photon-correlation spectroscopy or dynamic
light scattering. Photon-correlation spectroscopy requires the
viscosity of the medium to be known and determines the diame-
ter of the particle by Brownian motion and light scattering prop-
erties. The results obtained by photon-correlation spectroscopy
are usually verified by scanning or transmission electron mi-
16. Liu, C.; Angell, C.A. Solid State Ionics 1996, 467, 86–88.
17. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.;
Cheeseman, J.R.; Zakrzewski, V.G.; Montgomery, J.A. Jr.; Stratmann, R.E.;
Burant, J.C.; Dapprich, S.; Millam, J.M.; Daniels, A.D.; Kudin, K.N.;
Strain, M.C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.;
Mennucci, B.; Pomelti, C.; Adamo, C.S.; Clifford, Ochterski, J.; Petersson,
G.A.; Ayala, P.Y.; Cui, Q.; MoroKuma, K.; Malick, D.K.; Rabuck, A.D.;
Raghavachari, K.; Foresman, J.B.; Cioslowski, J.; Ortiz, J.V.; Stefanov,
B.B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Mar-
tin, R.L.; Fox, D.J.; Keith, T.; Al-Laham, M.A.; Peng, C.Y.; Nanayakkara,
A.; Gonzalez, C.; Challacombe, M.; Gill, P.M. W.; Johnson, B.; Chen, W.;
Wong, M.W.; Andres, J.L.; Head-Gordon, M.; Replogle, E.S.; Pople, J.A.
GAUSSIAN 98 (Revision A. 3); Gaussian Inc., Pittsburgh, PA, 1998.