ULTRASOUND ASSISTED SYNTHESIS, CHARACTERIZATION AND [601334]

Journal of Molecular Structure
Manuscript Draft

Manuscript Number: MOLSTRUC -D-16-00610

Title: ULTRASOUND ASSISTED SYNTHESIS, CHARACTERIZATION AND
ELECTROCHEMICAL STUDY OF A TE TRADENTATE OXOVANADIUM DIAZOMETHINE COMPLEX

Article Type: Research Paper

Keywords: Schiff base, Oxovanadium, Ultrasound Irradiation, X -ray
Diffraction, Cyclic Voltammetry.

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ULTRASOUND ASSISTED SYNTHESIS, CH ARACTERIZATION AND
ELECTROCHEMICAL STUDY OF A TETRADENTATE OXOVANADIUM
DIAZOMETHINE COMPLEX .
Moufida Merzouguia, Kamel Ouaria*, Jean Weissb
a Laboratoire d’ Electrochimie, d’Ingénierie Moléculaire et de Catalyse Redox (LEIMCR) , Facult é de
Technolog ie, Université Ferhat ABBAS Sétif-1, 19000 Sétif, Alg érie.
bLaboratoire de Chimie des Ligands à Architecture Contrôlée (CLAC), Institut de Chimie UMR 7177
CNRS -Université de Strasbourg, 1 rue Bl aise Pascal, 67008 Strasbourg C edex, France.
Abstract
The oxovanadium(IV) complex “VOL” of a tetradentate Schiff base ligand derived
from the condensation of diaminoethane and 2 -hydroxy -1-naphthaldehyde was efficiently
prepared via ultrasound irradiation and the template effect of VO(acac) 2.
The resulting product was characterized by elemental analysis, infrared, electron ic
absorption and molar conductance measurement . Single X -Ray str ucture analysis showed that
the complex is a monomeric five -coordinate with a distorted square pyr amidal geometry. It
crystallizes in monoclinic system having unit cell parameters a=8.3960(5) Å; b= 12.5533(8) Å
and c= 18.7804(11) Å; α = γ = 90°; β =104.843°(2), with P 2 1/c space group.
Cyclic voltammetry of the complex, carried out on a glassy carbon (GC) electrode in
DMF , show ed reversible cyclic voltammograms response in the potential range 0.15 –0.60 V
involving a single electron redox wave VV/VIV, the diffusion coefficient is determined using
GC rot ating disk electrode . The Levich plot, , was used to calculate the
diffusion -convect ion controlled currents.
Keywords: Schiff base, Oxovanadium , Ultrasound I rradiation , X-ray D iffraction, C yclic
Voltammetry .
Introduction
Schiff base ligands (SB) derived from dia mines and phenolic aldehydes have prove n to
be a class of versatile ligands for many transition metals including vanadium(IV) [1-3].
Recently, the coordination chemistry of vanadyl complexes has extraordinary developed in
various directions due to their interesting structural features [4 -6], catalytic applications [7]
potential roles in a variety of biorelated processes, such as insulin mimics [8 -9], as well as
antimicrobial or anti -leukemia effects [10 -11]. The presence of different heterocyclic moieties Manuscript
Click here to view linked References

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in some oxovanadium SB complexes h as been linked to their antitumoral properties confering
them a promising future in treatment of cancers [12].
The majority of oxovanadium (IV) SB complexes exhibiting N2O2 coordination and
reported in the literature are green. Their structure is generally well established as monomers
with five -coordinate square -pyramidal geometry [5, 6] but in rare cases, trigonal bipyramidal
or distorted octahedral geometries have been observed [13 -15]. Heterogeneous oxovanadium
SB complexes catalysts, immobilized in microspheres, have been successfully used in the
aerobic selective oxidation of ethyl benzene to acetophenone and e xhibit high catalytic
activity and excellent selectivity [16].
Electrochemical study and structural proprieties of oxovanadium complexes with
tetradentate SB ligands attract particular attention because of their reversible one -electron
redox behavior [17-18]. However , oxovanadium complexes with a large number of
tetradentate SB ligands have been wid ely reported [19-20].
Electrochemical study and structural properties of oxovanadium complexes bearing
tetradentate SB ligands have attracted particular attention owing to their two succe ssive one
electron redox couple [17 -18] and oxovanadium complexes with a large number of
tetradentate SB ligands have been widely reported [19 -20]. Over the last decades considerable
efforts have been aiming at the development of new synthetic procedures including the
solvent -free method [21], microwave assisted synthesis approach [22], electros ynthesis [23]
and ultrasound assisted synthesis [24]. Ultrasound irradiation is considered as a green and
efficient technique for the activation of reagents in the synthesis of organic [25 -26] and
inorganic compounds [27]. The formation of several metal co mplexes bearing azo ligands,
like Schiff bases [28-29], porphyrins [30] and quinolones [31], have been enhanced under
ultrasound. The significant features of the ultrasound approach are the formation of pure
products in prominent yields [32], the improved rate of reactions and the easier handling of
reagents and products. The ultrasound synthesis technique is thus highly adapted to green
chemistry approaches in coordination chemistry [33].
Considering the importance of oxovanadium SB complexes, we wish to report in this
work a safe procedure without solvent under ultrasound irradiat ion for the synthesis of an
oxovanad ium complex by template method, previously prepared by F.C. Anson [34] using a
conventional procedure. The complex has been characterized by single crystal X -ray
diffraction and the electrochemical properties of this complex have been investigated by

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cyclic voltammetry at a glassy carbon (GC) electrode in DMF solvent. The di ffusion
coefficient has been determined using the Levich plot on a GC rotating disk electrode.
1. Experimental
1.1. Materials and me asurements
All chemical reagents and solvents were purchased from Merck or Aldrich and used
without further purification. Sonication w as performed on an US-bath with frequency of 50 –
60 Hz and a nominal power (720 W). Elemental analyses were performed on an Elementar –
Vario EL III CHNS analyzer. Infrared spectra were obtained using potassium bromide (KBr)
pellets (4000 –400 cm-1) on a Shim adzu FTIR spectrophotometer. Electronic spectra in the
200–900 nm range were recorded using a Shimadzu UV -1800 spectrophotometer using DMF
as solvent. Molar conductance of VOL complex was determined in DMF (10-3 M) at room
temperature using Mete rLab CDM – 210 conductivity meter. Melting point of the complex
was determined on a Kofler Bank 7779 apparatus.
Electrochemical experiments were performed on a PGZ 301 potentiostat, cyclic
voltammograms (CV) and rotating disk Electrode (RDE) measurements we re recorded at
room temperature in DMF solution s containing 0.1 M LiClO 4 as supporting electrolyte, using
a glassy carbon (GC) as working electrode, platinum wire and a saturated calomel electrode
(SCE) were used as counter and reference electrodes, respectively. Prior to the experiments
the working electrode was polish ed and rinsed thoroughly with distilled water and acetone.
The polished electrode was placed in 0.5 M H 2SO 4 solution and the electrochemical activation
of the electrodes were performed by continuous potential cycling from -500 to 1800 mV at a
sweep rate of 100 mV s-1 until a stable voltammogram is obtained [35]. Before each
electrochemical investigation, the electrolyte was purged with nitrogen during 15 minutes.
Cyclic voltammogram measurements were performed in the range -2200 to 1600 mV
versus SCE in which the electrochemical redox couple of VIV/VV is observed in the positive
window of the scan. Under identical condition s, the ferrocene/ferrici nium (Fc/Fc+) couple is
observed at 455 mV.
1.2. Synthesis procedures
1.2.1. Ultrasonication method
A reaction flask containing 0.344 g (2 mmol) of 2 -hydroxy -1-naphthaldehyde, 66.8 µl
(1 mmol) of 1,2 -diaminoethane and 0.265 g (1 mmol) of bis (acetylacetonato) oxovanadium
(Scheme.1 ), mixed in a mortar , was immersed in an ultrasonic bath at a temperature o f 50 °C.

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The reaction mixture was exposed to ultrasound irradiation for 40 min. Upon reaction
completion shown by TLC analysis (silica gel, CH 2Cl2/MeOH, 9.5/0.5, V/V) , the obtained
product was washed with methanol (3x3ml) and diethylether (3x3ml) and filte red. Single
crystals, suitable for X -ray diffraction, were obtained after 2 days of crystallization from
DMSO/MeOH. Color: green, Yield: 95 .4 %, mp: >270°.
O
OHH2N NH2N
ON
OH H
V
O2 VO(acac)2 +
Solvent-free)))+50°C
+

Scheme 1. Synthesis of the oxovanadium complex (VOL).
1.2.2. Conventional method
To a solution of 0. 344 g (2 mmol) of 2 -hydroxy -1-naphthaldehyde in 8 ml of methanol
was added 66.8 µl (1 mmol) of 1,2 -diaminoethane in 5ml of methanol. 0.265 g (1 mmol) of bis
(acetylacetonato) oxovanadium dissolved in 15 ml of methanol was added drop wise. The
reaction was stirred and refluxed for 3 hours under nitrogen atmosphere. Reaction complete ,
based on TLC analysis, the resulting compound was filtered and washed with methanol and
diethylether to afford pure des ired product yielding 77.6%. S.A. A mer [36 ], N. Choudhary
[37] and F.C. Anson [ 34-38] have reported the synthesis of this complex yielding 70-90%.
Both oxovanadium complexes gave satisfactory elemental analysis complex in good
agreement with calculated values . Analysis calculated for C 24H18N2O3V: C: 66.52%, H:
4.19%, N: 6.46% ; found: C: 66.83% ; H:4.35 %; N: 6.32 % ; IR (KBr pellets  cm-1) 1618
(C=N),1340 -1360 (C -O),1542 (C=C), 983 (V=O); UV -Vis: DMF, λ nm,[ε M-1 cm-1]:
323[7722], 380[4166], 610 [83].
1.3. X-ray crystallography
Suitable single crystals of the oxovanadium complex (VOL) were grown by slow layer
diffusion of DMSO into a MeOH solution at room temperature. A green plate single crystal of
dimensions 0.25x 0.18x 0.12 mm3 suitable for X -ray analysis was used for data collection at
173(2) K on a Bruker APEX II DUO Kappa -CCD diffractometer equipped with an Oxford
Cryosystem liquid device, using Mo/Kα radiation (α = 0.71073Å). The crystal -detector
distance was 38 mm.
The ce ll parameters were determined (APEX2 software) [39] from reflections taken
from three sets of 12 frames, each at 10s exposure. The structure was solved by direct

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methods using the program SHELXS -97 [40]. The refinement and all further calculations
were car ried out using SHELXL -2013 [41]. The H -atoms were included in calculated
positions and treated as riding atoms using SHELXL default parameters. The non -H atoms
were refined anisotropically, using weighted full -matrix least -squares on F2. A semi -empirical
absorption correction was applied using SADABS in APEX2 [39]; transmission factors:
Tmin/Tmax = 0.6157/0.7456.
1.4. Results and discussion
1.4.1. Molar Conductance
The molar conductance of 10-3 M of VOL complex in DMF as solvent is Λ=1.74 Ω-1
cm² mol-1, this very low value indicating that the title compl ex is electritically neutral [42-43].
1.4.2. Crystal structure of VOL complex
The crystal structure of the complex, depicted in Fig. 1, consists of one molecul e in the
asymmetric unit. The compound crystallizes in the monoclinic system with space group
P21/c and the cell dimensions a=8.3960 (5); b= 12.5533 (8); c= 18.7804 (11) Å; α = γ = 90°;
β =104.843° (2).

Fig. 1. ORTEP plot of the X -ray crystal structure of VOL complex with atom labeling
scheme . Displacement ellipsoids are drawn at the 50% probability level except for the H
atoms, which are shown as circles of arbitrary radius.

Parameters for data collection and refinement are summarized in Table 1. Selected bond
lengt hs and angles are listed in Table 2.
Table 1
Crystallographic and refinement data of VOL complex
Compound VOL
Molecular formula moiety
Molecular weight
Temperature (K) C24 H18 N2 O3 V
433.34
173(2)

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Radiation
Crystal system
Space group
a/ Å
b/ Å
c/ Å
Alpha
Beta
Gamma
V/ Å3
Z
Dcalc (g.cm-3)
Crystal size (mm3)
Crystal color
Crystal description
Absorption coefficient
F(000)
Reflections collected/unique
Ranges/ indices (h; k; l)
Teta limit
No. of observed data [I > 2 σ(I)]
No. of parameters
No. of restraints
Goodness -of-fit on F2
Largest diff, peak and hole (eÅ-3)
R1, wR 2 [I ≥ 2σ(I)]a
R1, wR 2 (all data)a Mo Kα 0.71073Å
Monoclinic
P21/C
8.3960(5)
12.5533 (8)
18.7804(11)
90.00
104.843 (2)
90.00
1913.4 (2)
4
1.504
0.25, 0.18, 0.12
Green
Plate
0.549
892
19012/4639 [R int = 0.0526]
-11,11; -16,16; -24,24
1.972 -28.110
3296
271
0
1.011
0.512 and -0.317
0.0699, 0.0930
0.0384, 0.0828
a ,
where

Table 2
Selected bond lenghts (Å), and bond angles (°) for VOLet complex.
Bond lenghts (Å) Bond angles (°)
V1-N1 2.0367 (16) O1-V1-O2 89.21 (6) O1-V1-O3 107.09 (7)
V1-O1 1.9491 (14) O1-V1-N1 85.41 (6) O1-V1-N2 148.88 (6)
V1-O3 1.5951 (14) O2-V1-O3 111.75 (7) O2-V1-N1 140.29(6)
V1-N2 2.0401 (16) O2-V1-N2 85.83 (6) O3-V1-N1 107.42 (7)
V1-O2 1.9324 (14) O3-V1-N2 103.27 (7) N1-V1-N2 79.12 (6)

The structure of the VOL complex has a slightly distorted square pyramidal
coordination geometry. The basal square plane is formed by the N,N’ -bis (2 -hydroxy –

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naphthalidenato) – diaminoethane molecule, which acts as a tetradentate ligand through its two
N atoms and two deprotonated phenol O atoms. The two naphthalene rings are near ly
coplanar with a dihedral angle of 2.315(41)° between the two rings . Typical values of V-N
bond distances of 2.0367(16) and 2.0401(16) Å, and V-O bond distances of 1.9491(14) and
1.9324(14) Å, are found in agreement with those reported for other oxovanad ium (IV)
complex [ 44]. The V1 -O3 bond distance is 1.5951(14) Å and the V1 atom is located 0.596 Å
above the mean pla ne defined by atoms N1/N2/O1/O2 . In the cell, the crystal is stabilized by
a net work of intermolecular hydrogen bonds, which are shown in Fi g. 2. There are no other
intramolecular interactions in the structure.

Fig. 2. Crystal packing of VOL complex showing intermolecular hydrogen bonds
as dashed lines.
1.4.3. FTIR spectra
The IR spectrum of the VOL complex exhibits several prominent bands in the 4000–
400 cm-1 region. Among these absorptions, t he VOL complex displayed strong C=N stretch
(around 1618 cm-1) which indicates the C=N group of the co ordinated SB ligand [45]. It can
be noticed that ν C=N band in the complex is shifted to the lower energy region of
approximately 20 cm-1 in the corresponding free ligan d reported in the literature [46-47].
Another broad band around 1540 cm-1 is related to the aromatic C=C vibration [ 1]. In
addition , the stre tching vibration of C -O, in the naphtholate moities , at 1340 -1360 cm-1
suggests the coordination of the naphtholate oxygen to the vanadium ion a s reported in the
literature [46], this absorption frequency is higher than that observed in the spectrum of
corresponding ligand ( 1327 cm-1) [48-49].

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The complex exhibits characteristic sharp and medium ν(V=O) at 987 cm-1 indicating
that there is no intermolecular interaction with the participation of the oxovana dium moiety
[2-10].
1.4.4. Electronic spectroscopy
The electronic spectrum of the oxovanadium complex was recorded using DMF
solution at room temper ature in the range 200 -800 nm. The complex showed two intense
bands at 323 and 380 nm that can be assigned to π→π* transitions of the aromatic rings of
naphthalene and n →π* transitions of the azomethine chromophore s respectively [ 50]. A
broad s houlder is observed near 400 nm correspondi ng to the ligand -to-metal charge -transfer
transition (LMCT) , from the lone pair system of both O-atoms in naphthalene rings to the d
orbital of the vanadium atom [ 19].The vanadium (IV) complex exhibits an additional low
intensity broad band in the range of 550-800 nm due to d →d transitions [5]. The UV-vis
absorption spectrum of VOL complex is shown in Fig. 3.

Fig. 3. UV–vis absorption spectra of VOL complex in DMF at room temperature, the
inset shows an expanded spectrum between 450 and 800 nm.
1.4.5. Electrochemical
The redox prop erties of the SB ligand and its oxovanadium complex were investigated
by cyclic voltammetry under nitrogen atmosphere, using DMF solution containing 0.1 M
LiClO 4 as supporting electrolyte, at a glassy carbon as a working elec trode, the redox

9
potentials are expressed with reference to SCE. The cyclic voltammograms are given in Fig.
4.

Fig. 4. Cyclic voltammogram s of VOL complex (a), SB ligand (b) and Fc/Fc+
(c) in 0.1 M LiClO 4/DMF solution at scan rate of 100 mV s-1.
The cyclic voltammogram of the VOL complex showed three anodic waves at
=+1125, = +415 and =-1659 mV/SCE. The first anodic wave is irreversible and
assigned to the oxidation of the ligand [19]. The second and the third ones are quasi -reversible
redox system s showing the half wave potentials at =+374 and = -1704 mV/ SCE . The
peak -to-peak separation between the anodic and the cathodic potentials , and , are of
82 and 90 mV respectively [ 51-52] at 100 mVs-1 scan rate . The half wave potentials =
+374and = -1704mV/ SCE are assigned to the VOV/VOIV and VOIV/VOIII redox
processes, similar compound s are widely reported in the literature. [17, 53-54].The reduction
wave occurred at = -1537 mV/SCE is due to the red uction of the azomethine groups . [55]
In the free ligand , two irreversible waves are observed on its cyclic voltammogram , an
anodic wave appearing at +1116 mV/SCE and a cathodic one at -1653 mV/SCE attributed
respectively to the oxidation of the hydroxyl functions and the reduction of the azomet hine
groups as reported in the literature [56, 57]. The oxidation and the reduction peak potentials
of the ligand are shifted to a slightly lowe r potential values , reveals that the hydroxyl (-OH)
and the azomet hine( C=N ) group s are involved in the binding of the vanadyl core . [58]

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Table 3
Cyclic voltammetric parameters for the oxovanadium SB complex in different scan rates
v ipa/ipc
50 415 335 80 375 10.33 10.13 1.01
100 415 333 82 374 14.66 14.35 1.02
150 417 335 82 376 18.11 17.2 1.05
200 418 334 84 376 20.54 19.56 1.05
250 420 334 86 377 22.79 22.49 1.01
300 422 332 90 377 25.35 25.22 1.01
350 423 331 92 377 26.56 25.79 1.03
400 424 330 94 377 28.24 27.76 1.02

Cyclic voltamm ogram measurements at different sca n rates , between 50 and 4 00 mV s-1
(Fig. 5 ) indicate , in the potential range of 150 – 600 mV/SCE, that values are slightly
dependent upon the scan rate . By increasing the scan rate values, t he anodic and the cathodic
peak potentials shift respectively to a more positive and a more negative value s. The ratios of
the anodic to cathodic peak ipa/ipc currents are close to unity (Table 3). The peak separation
between the cathodic and the anodic peak potentials , , have been determined, and reach a
value of 82 mV at 100 mV s-1 scan rate that is greater than that expected for reversible
systems , which indicates a quasi -reversible electrode process . Similar results have been
reported for several oxovanadium SB complexes [12, 17]. A linear relationship b etween the
anodic peak current and the square root of the scan rates (ipa = f(v1/2)) is observed (inset of
Fig. 5), this fact implies that this electrochemical process is mainly diffusion -controlled [ 6,
59].

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Fig. 5. Cyclic voltammograms of VOL complex in 0.1 M LiClO 4/DMF solution at
various scan rates: from inner to outer, 50, 100, 150, 200, 250, 300, 350 and 400 (mVs-1)
respectively. The inset shows the anodic currents vs v1/2.
In order to determine the diffusion coefficient, a hydrodynamic voltammetry experiment
is carried out using a glassy carbon rotating disk electrode ( RDE ) at various rotation rates,
from 250 to 3000 rpm . The experiment is realized in DMF solution containing 1 mmol of
VOL complex and 0.1 M LiClO 4. The current –potential curves and the Levich plot s are
shown are in Fig. 6. Under the studied conditions, a linear correlation between the limiting
current and the square root of the rotating rate is observed which leads to the determination of
the value of the proportionality constant in the Levich equation for a one electron VOV/VOIV
reduction [ 60]. Diffusion coefficient was calculated to be ( 2.7.10-6 cm²/s) from the slopes of
the i lim vs. ω1/2 plots, using Levich equation [ 61]:

where i lim is the Levich current ( A/cm²), n is the number of electrons transferred, F is
the faraday constant (C/mol), A is the electrode area (cm²), υ is the kinematic viscosity
(cm²/s), D and C are the diffusion coefficient (m²/s) and the analyte concentration (mol/cm3)
respectively, ω is the angular rotation rate of the electrode (rad/s).

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Fig. 6. Voltamm ograms of VOL complex at RDE in 0.1 M LiClO 4/DMF solution .
Rotation rates : from 250 to 3000 rpm. The inset shows the Levich plot .
Conclusion
In this paper, we describe the sonochemi cal and conventional synthesis of a
symmetrical oxovanadium Schiff base complex. In free solvent condition s, the ultrasonic
irradiation procedure reduce s the reaction time to 40 minutes instead of 3 hours compared
with the conventional method and affords t he desired product in a higher yield and purity. The
non-electrolytic nature of the VOL complex was confirmed on the basis of their molar
conductance value. The crystallographic data showed that the vanadium (IV) ion in VOL
Schiff base complex is five coor dinated with distorted square -pyramid geometry.
The electrochemical behavior of the complex exhibits a quasi -reversible one electron
redox process at E 1/2=374 mV/SCE , with current ratio i pa/ipc equals to unity and the peak -to-
peak separation value, Ep, is of 82 mV. The linear relationship observed between the anodic
peak current (i pa) and the square root of the scan rates (v1/2) indicates a diffusion -controlled
nature of the electrode process. The d iffusion coefficient is 2.5.10-6 cm²/s from the Levich
plots, I lim = f(ω1/2).

Supplementary data

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CCDC 1003714 contain s the supplementary crystallographic data for VOL. These data
can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html , or from
the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223 -336-033; or e -mail: deposit@ccdc.cam.ac.uk .
Acknowledgeme nts
The Authors gratefully acknowledge the financial support from The Algerian Ministry
of Higher Education and Scientific Research. They also acknowledge the help to access the
NMR Facility and Microanalysis Service at the Chemistry Institute of the Universit y of
Strasbourg – France.
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