IJIRST –International Journal for Innovative Research in Science & Technology| Volume 3 | Issue 12 | May 2017

ISSN (online): 2349-6010

XAFS Study of Copper (II) Complexes of P-

Anisidine
Jaishree Bhale Pradeep Sharma
Shree Cloth Market Institute of Professional Studies, Govt. Holkar Science College, Indore(M.P),
Indore(M.P), India India.

A.Mishra
School of Physics, DAVV, Indore(M.P), India

Abstract
X-ray K-absorption spectroscopic studies have been carried out on three copper (II) mixed-ligand complexes .The complexes are
[Cu(L6)2(H2O)2(Cl)](0.2)H2O, [Cu(L6)2(H2O)2(SO4)](0.2)H2O and [Cu(L6)2(H2O)2(Br)](0.2)H2O where ligand L6= (p-
methoxy anilino) –P– chloro phenyl acetonitrile. XAFS spectra have been recorded at the K-edge of Cu using the dispersive
beam line at 2.5GeV Indus-2 synchrotron radiation source RRCAT(Raja Ramanna Center for Advance Technology ), Indore,
India. The data obtained has been processed using XAFS data analysis program Athena and the computer software Origin 6.0
professional. Various X-ray absorption parameters e.g., chemical shift, edge-width and shift of the principal absorption
maximum have been obtained in the present study. The chemical shift data have been utilized to estimate effective nuclear
charge on the absorbing atom. Further the observed chemical shifts have been correlated with percentage covalency in these
complexes. The studies establish significant correlation between various parameters for these complexes. The XAFS data
obtained has also been used to determine the bond length by using four different methods, i.e., Levy’s, Lytle, Lytle, Sayers and
Stern’s (LSS) and Fourier transformation methods. The results of the study have been reported in this paper.
Keywords: Compatibility, Superplasticizers, Silica fume
________________________________________________________________________________________________________

I. INTRODUCTION

X-ray absorption fine structure (XAFS) refers to the details of how x-rays are absorbed by an atom at energies near and above
the core-level binding energies of that atom. Specifically, XAFS is the modulation of an atom’s x-ray absorption probability due
to the chemical and physical state of the atom. The x-ray absorption spectrum is typically divided into two regimes: X-ray
absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure spectroscopy (EXAFS).
X-ray absorption spectroscopy has been extensively used to obtain information about the molecular structure viz. the oxidation
state and the effective nuclear charge of the absorbing atom in compounds and complexes.
The Fourier transform of an EXAFS spectrum provides information on the distribution of atomic shells as a function of
distance from the target absorber. The bond lengths have also been determined by three graphical methods, namely, Levy’s [1],
Lytle’s [2], and Lytle, Sayers and Stern’s (LSS) [3, 4]methods. The results of the comparative study have also been reported in
this paper.
XANES and EXAFS studies of some of the copper (II) complexes of p-anisidine have been already discussed in previous
literature [5-7]. The XAFS characterization of some more complexes had been carried out and their results have been reported in
this paper.

II. EXPERIMENTAL DETAILS

The three complexes studied in the present investigations are [Cu(L6)2(H2O)2(Cl)](0.2)H2O, [Cu(L6)2(H2O)2(SO4)](0.2)H2O
and [Cu(L6)2(H2O)2(Br)](0.2)H2O .The ligand L6= (p-methoxy anilino) –P– chloro phenyl acetonitrile was synthesized. The
ligand was prepared by Strecker's procedure [8 -9] which included the reaction of p-chlorobenzaldehyde with p-anisidine. All the
complexes were prepared according to the standard methods reported in literature and their purity was checked [10]. The X-ray
absorption spectra at the K-edge of copper of these complexes have been recorded at BL-8 Dispersive EXAFS beamline at the
2.5-GeV INDUS-2 Synchrotron Source, Raja Ramanna Centre for Advanced Technology (RRCAT), Indore, India [11 - 13]. The
experimental data have been analyzed using the available computer software packages Origin 6.0 professional and Athena [14].
Table – 1
Abbreviation and molecular formulae of copper (II) complexes
Complexes Abbreviation Molecular formulae
I [Cu(L6)2(H2O)2(Cl)](0.2)H2O [Cu(C15H14N2 OCl )2(Cl)2] 0.2H2O
II [Cu(L6)) 2 (H 2O) 2(SO 4)](0.2)H2O [Cu(C15H14N2OCl)2(SO4)2] 0.2H2O

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III [Cu(L6)2(H2O)2(Br)](0.2)H2O [Cu(C15H14N2 OCl )2(Br)2] 0.2H2O

Fig 1. The XANES region of the absorption spectrum at the K-edge of copper metal and in the complexes indicating positions of the absorption
edge K and the principal absorption maxima A.

Fig. 2. Derivative of the XANES region of the absorption spectrum at the K-edge of copper metal and in the complexes indicating positions of
the absorption edge K and the principal absorption maxima A.

Table – 2
XANES data for the K absorption edge of copper in the complexes.
Shift of the principal Edge-width ENC
EK EA Chemical shift %
Complexes absorption maximum (EA_EK) Electron/
(eV) (eV) (eV) Covalency
(eV) (eV) atom
Copper metal 8980.12 8996.21 - - 16.088 - -
[Cu(L6)2(H2O)2(Cl)](0.2)H2O 8986.99 8998.30 6.87 2.09 11.31 0.71 65.15

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[Cu(L6)2(H2O)2(SO4)](0.2)H2O 8988.37 8997.78 8.32 3.55 9.41 0.82 55.45

[Cu(L6)2(H2O)2(Br)](0.2)H2O 8990.22 9001.55 10.10 5.34 11.33 0.95 35.65

III. RESULTS AND DISCUSSION

The shapes of the copper K-absorption discontinuity and the associated near edge structure (XANES) for all the complexes are
shown in Fig 1.The curves in this figure represent the normalized K absorption spectra. The energies of the copper K-edge (EK)
and the principal absorption maximum (E A) along with the values of the edge-width (EA-EK), effective nuclear charge Zeff and the
chemical shift ΔEK are given in Table 2.
The EXAFS spectra converted into k space have been given in Figure 6. The values of energy E and wave vector k
corresponding to these maxima and minima have been shown in Table 3. The slopes of energy level Q Vs energy E curves,
shown in Figure 7, have been used to evaluate the bond length by Lytle method. The slopes of channel number n Vs wave vector
k curves, shown in Figure 8, have been used to evaluate the bond length by LSS method. The magnitudes of Fourier transform of
Figure 6 are shown in Figure 9.

Chemical Shift
The shifts of the K-absorption edge of copper in the complexes with respect to that of copper metal have been determined
according to the eqn.
ΔEK = EK(complex) - EK(metal)
The results are given in Table 2. For computing the chemical shift, the value of EK (Cu metal) has been taken as 8980.12 eV.
For the complexes under study, the order in which the ligands contribute to the chemical shift is:
[Cu(L6)2(H2O)2(Br)](0.2)H2O > [Cu(L6)2(H2O)2(SO4)](0.2)H2O > [Cu(L6)2(H2O)2(Cl)](0.2)H2O
In Table 2, the complexes have the values of chemical shifts as 6.87, 8.32 and 10.10 eV. Hence, on the basis of values of the
chemical shifts, the complexes are found to have copper in oxidation state +2 [15].
As compared to the K-absorption edge in the metal, the K-absorption edge of copper has been found to be shifted towards the
high-energy side in all the complexes studied.

IV. EFFECTIVE NUCLEAR CHARGE AND CHEMICAL SHIFT

In the present work, Zeff has been obtained from the measured chemical shift by using the semi-experimental method by
employing the procedure suggested by Nigam and Gupta [16]. The data is presented in Table 2. The effective nuclear charge on
the copper in the complexes under present study varies between 0.71 – 0.95 electrons/atom. An attempt was made to establish a
co–relation between ENC and chemical shift. A parabolic co–relation is observed between them. The results show that chemical
shift increases then ENC also increases.

10
Chem ical shift eV

5
0 .5 1

E N C e le c tro n /a to m

Fig. 3: Correlation between ENC and chemical shift

Percentage Covalence and Chemical Shift

To calculate the percentage covalency of the bonds, a theoretical graph is plotted between the calculated value of binding energy
of 1s electron using Clementi’s results of atomic function and percentage covalency for copper [17]. An attempt was made to
establish a co–relation between percentage covalency and chemical shift. A parabolic co–relation is observed between them .It is
clear from the Table 2 that the chemical shift decreases as the percentage covalency increases.

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 XAFS Study of Copper (II) Complexes of P-Anisidine
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10

C hem ical shift (eV ) 5

40 70

P e rc e n ta g e c o v a le n c y

Fig. 4: Correlation between percentage covalency and chemical shift

V. PERCENTAGE COVALENCY AND ENC

It is clear from the data that the percentage covalency increases as effective charge decreases. . A parabolic co–relation is
observed between them.

1
ENC electron/atom

0 .5
40 70

P e rc e n ta g e c o v a le n c y

Fig. 5: Correlation between percentage covalency and ENC

Principal Absorption Maximum

The data for the principal absorption maximum EA for the complexes is also included in Table II.
The shifts of the principal absorption maximum at the K-absorption edge of copper in the complexes with respect to that of
copper metal have been determined according to the eqn.
ΔEA = EA(complex) – EA(metal)
For computing the chemical shift the value of EA(Cu metal) has been taken as 8996.21 eV.
It has been observed that the value of EA is shifted towards the higher energy side with respect to copper metal [18].

EDGE-WIDTH
In Table.2 the values of the edge-width (EA-EK) have been reported. The experimental data of edge-width of Cu (II) complexes
(Table 2) show that the edge-width decreases as follows:
[Cu(L6)2(H2O)2(SO4)](0.2)H2O < [Cu(L6)2(H2O)2(Cl)](0.2)H2O < [Cu(L6)2(H2O)2(Br)](0.2)H2O

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 XAFS Study of Copper (II) Complexes of P-Anisidine
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Fig. 6: χ (k) versus k curves for the copper complexes

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 XAFS Study of Copper (II) Complexes of P-Anisidine
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[Cu(L6)2(H2O )2(Cl)](0.2)H2O
[Cu(L6)2(H2O )2(Br)](0.2)H2O
[C u(L6)2(H 2O )2(S O 4)](0.2)H 2O
6
6

8
5
5

4
4 6

3 3
n

n
4

n
2 2

2
1 1

0 0 0

2 3 4 5 6 7 8 9 10 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
-1 -1
k(Å ) K(Å ) -1
k(Å )

Fig. 7: n versus k curves for the copper complexes

[C u(L6)2(H 2O )2(C l)](0.2)H 2O

160 [Cu(L6)2(H2O)2(SO4)](0.2)H2O
[C u(L6)2(H 2O )2(B r)](0.2)H 2O
250
140
250

120
200
200

100

150 150
80

E
E

100 60
100

40
50

50
20
0

0
0
2 4 6 8 10 12 2 4 6 8 10 12
2 4 6 8 10 12

Q Q Q

Fig. 8: Q versus E curves for the copper complexes

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 XAFS Study of Copper (II) Complexes of P-Anisidine
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Fig. 9: Magnitude of Fourier transform of the χ(k) versus k curve for Cu(II) complexes

Table – 3
Energy E (eV) and wave vector k (Å-1) for EXAFS maxima and minima at the K absorption edge of copper in the complexes and their
corresponding values of n and energy level Q
[Cu(L6)2(H2O)2(Cl)](0.2)H2O [Cu(L6)2(H2O)2(SO4)](0.2)H2O [Cu(L6)2(H2O)2(Br)](0.2)H2O
Structure n Q
E (eV) k (Å-1) E (eV) k (Å-1) E (eV) k (Å-1)
A 0 2.04 19.249 2.25 13.01 1.85 18.403 2.2
α 1 - 54.904 3.80 38.93 3.2 43.954 3.4
B 2 6.04 127.908 5.80 63.91 4.1 63.916 4.1
β 3 - 240.313 7.95 108.83 5.35 93.165 4.95
C 4 12.0 291.112 8.75 146.15 6.2 119.239 5.6
γ 5 - - - - - 160.646 6.5
Table – 4
Values of first shell bond lengths (in Å) calculated from Levy’s, Lytle’s, LSS and Fourier transform methods for the copper (II) complexes
Complexes Levy’s method Lytle’s method LSS method Fourier transform
[Cu(L6)2(H2O)2(Cl)](0.2)H2O 2.09 1.87 1.50 1.48
[Cu(L6)2(H2O)2(SO4)](0.2)H2O 2.0 1.67 1.43 1.41
[Cu(L6)2(H2O)2(Br)](0.2)H2O 2.24 1.06 1.16 1.46

VI. CONCLUSIONS

X-ray absorption spectra of mixed ligand copper complexes at the K-edge of copper have been recorded at the recently
developed EXAFS beamline setup at the Indus-2 synchrotron source at RRCAT, Indore. The energy of K-edge (EK), and
principal absorption maxima (EA) have been reported. From these, the shift of the K-edge (chemical shift), shift of the principal
absorption maximum and edge-width has been obtained. The chemical shift has been used to determine the effective nuclear
charge on the absorbing atom and percentage covalency. The values of the chemical shifts suggest that copper is in oxidation
state +2 in all of the complexes.

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 XAFS Study of Copper (II) Complexes of P-Anisidine
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From the positions of the EXAFS maxima and minima, the bond lengths in the complexes have been determined by three
different methods viz. Levy’s, Lytle’s and LSS methods. From the Fourier transforms of the EXAFS spectra, the bond lengths
(uncorrected for phase shift) have been determined. It has been observed that the values of the phase-uncorrected bond length,
i.e. R1-α1, as determined from LSS method and that determined from the Fourier transformation method, agree with each other
within the limits of experimental error.

ACKNOWLEDGEMENT

The authors are thankful to Dr. S. N. Jha for his help in recording the spectra. The authors are also grateful to Mr. Nihar Patel
(Prashant group of industries) for his valuable support for this research work.

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