Ijirstv3i12021

IJIRST –International Journal for Innovative Research in Science & Technology| Volume 3 | Issue 12 | May 2017 ISSN (online): 2349-6010

Extended Fine Structure of the X-ray KAbsorption Discontinuity in Some Copper(II) Mixed Ligand Complexes of Benz Aldehyde Jaishree Bhale Shree Cloth Market Institute of Professional Studies, Indore (M.P), India

Pradeep Sharma Govt. Holkar Science College, Indore (M.P), India.

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

Abstract Cu K-edge extended X-ray absorption fine structure(EXAFS) spectra have been obtained for four copper (II) mixed ligand complexes using BL-8 Dispersive Extended X-ray Absorption Fine Structure (EXAFS) beamline at the 2.5-GeV INDUS-2 Synchrotron Source, RRCAT(Raja Ramanna Center for Advance Technology),Indore, India. The complexes are [Cu(ben)(pTol)(Cl)2], [Cu(ben)(p-Tol)(CH3COO)2], [Cu(ben)(p-Tol)(NO3)2] and [Cu(ben)(p-Tol)(Br)2]. The ligand (p-methyl anilino) phenyl acetonitrile was prepared which included the reaction of benzaldehyde with P-toluidine. The data obtained has been processed using EXAFS data analysis program Athena and the computer software Origin 6.0 professional. EXAFS maxima and minima positions have been obtained from the normalized spectra. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length .This distance is the phase-uncorrected bond length and has also been determined by Lytle, Sayers and Stern s (LSS) graphical method. It is found that the results obtained from LSS and the Fourier transformation methods are in good agreement with each other, i.e. both the LSS method and Fourier transformation method give nearly the same value of the phase-uncorrected bond lengths. In this paper, the first shell bond length has also been estimated by Lytle’s and Levy’s methods from the EXAFS data.

Keywords: Copper (II) mixed ligand complexes, EXAFS spectra, benzaldehyde, P-toluidine, normalized spectra _______________________________________________________________________________________________________ I.

INTRODUCTION

The chemistry of nitrile and α-aminonitrile compounds and their derivatives has received special attention because of their application as potential ligands for a large number of metal ions (1).Nitriles and α-aminonitrile derivatives had biological activities (2) as herbicides (3), pharmacological agents (4) and biological synthesis of chemical compounds by its microbial metabolism in some organisms (5). Aminonitrile compounds are well known to be biologically active species such as pharmaceutical interest and biocatyalysis in industrial synthesis [6] – [8]. Beside that they were used as synthetic activating transcription for the explanation of biological reaction [9] and identified as biologically inhibitors [10] – [13]. Furthermore aminonitrile is potentially a chelating ligand [14], [15]. These α-amino nitriles were synthesized by a modified Strecker’s procedure [16], [17].

The Extended X-ray Absorption Fine Structure (EXAFS) yields information regarding the nearest neighbors of the central metal ions, i.e. bond length. The Fourier transform of an EXAFS spectrum provides information on the distribution of atomic shells as a function of distance from the target absorber. These distances are called phase uncorrected bond lengths. The bond lengths can also be determined by three other methods, namely, Levy’s [18], Lytle’s [19], and Lytle, Sayers and Stern’s (LSS) methods [20, 21]. The LSS method also gives phase uncorrected bond length of the first shell. Hence, it is worth comparing the bond lengths obtained from LSS method with those obtained from Fourier transformation method.

XANES studies of some of the Cu(II) complexes of benzaldehyde have been already discussed in previous literature [22][23]. The EXAFS characterization of these complexes had been carried out and their results have been reported in this paper.

II. MATERIALS AND METHODS The four complexes studied in the present investigations are Cu(ben)(p-Tol)(Br)2 , Cu(ben)(p-Tol)(Cl)2, Cu(ben)(p-Tol) (CH3COO)2 and Cu(ben)(p-Tol)(NO3)2 where ben = benzaldehyde and p-Tol = p-toluidine . These four complexes were synthesized according to the standard methods reported in literature and their purity was checked [24]. The ligand L= (p-methyl anilino) phenyl acetonitrile was synthesized by Strecker's procedure [25,26] which included the reaction of benzaldehyde with ptoluidine. The X-ray absorption spectra at the K-edge of copper of these complexes have been recorded at BL-8 Dispersive

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Extended Fine Structure of the X-ray K-Absorption Discontinuity in Some Copper(II) Mixed Ligand Complexes of Benz Aldehyde (IJIRST/ Volume 3 / Issue 12/ 017)

EXAFS beamline at the 2.5-GeV INDUS-2 Synchrotron Source, Raja Ramanna Centre for Advanced Technology (RRCAT), Indore, India [27-29]. The digital records were analyzed using computer programs Origin and Athena [30].

Table – 1 Abbrevation and molecular formulae of copper (II) complexes Complexes Abbreviation Molecular formulae I [Cu(ben)(p-Tol)(Cl)2] [Cu(C15H14N2 )2(Cl)2] 0.2H2O II [Cu(ben)(p-Tol) (CH3COO)2] [Cu(C15H14N2 )2(CH3COO)2] 0.2H2O III [Cu(ben)(p-Tol)(NO3)2] [Cu(C15H14N2 )2(NO3)2]0.2H2O IV [Cu(ben)(p-Tol)(Br)2] [Cu(C15H14N2 )2(Br)2] 0.2H2O

III. RESULTS AND DISCUSSION The EXAFS appearing on high-energy side of the K absorption edge have been recorded in all the copper complexes, using the synchrotron DEXAFS beamline setup. The positions of the EXAFS maxima and minima in eV and their corresponding values of k in Å-1 are given in Table 2.

The normalized X-ray absorption spectra of copper complexes are shown in Figure.1.The EXAFS spectra converted into k space have been given in Figure 2. The values of energy E and wave vector k corresponding to these maxima and minima have been shown in Table 2. The slopes of energy level Q Vs energy E curves, shown in Figure 3, have been used to evaluate the bond length by Lytle method. The slope of channel number n Vs wave vector k curves, shown in Figure 4, have been used to evaluate the bond length by LSS method. The magnitudes of Fourier transform of Figure 2 are shown in Figure 5. The bond lengths estimated by these methods are tabulated in Table 3.

Table - 2 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(ben)(p-Tol) [Cu(ben)(p-Tol) [Cu(ben)(p-Tol) (NO3) 2] [Cu(ben)(p-Tol) (CH3COO) 2] (Cl) 2] (Br) 2] Structure n Q E k E k E k E k (eV) (Å-1) (eV) (Å-1) (eV) (Å-1) (eV) (Å-1) A 0 2.04 19.249 2.25 18.403 2.2 3.431 0.95 15,209 2.0 α 1 54.904 3.8 43.954 3.4 38.935 3.2 34.220 3.0 B 2 6.04 127.908 5.8 63.916 4.1 91.292 4.9 62.366 4.05 β 3 240.313 7.95 93.165 4.95 127.908 5.8 95.057 5.0 C 4 12.0 291.112 8.75 119.239 5.6 261.939 8.3 141.482 6.1 γ 5 160.646 6.5 339.553 9.45 -

Fig. 1: The normalized XAFS spectrum of copper complexes. The different spectra have been shifted vertically for better presentation.

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Extended Fine Structure of the X-ray K-Absorption Discontinuity in Some Copper(II) Mixed Ligand Complexes of Benz Aldehyde (IJIRST/ Volume 3 / Issue 12/ 017)

[C u (b e n )(p -T o l)(C H 3 C O O ) 2 ] 0

kchi(k)

[C u (b e n )(p -T o l)(N O 3 ) 2 ] -2

[C u (b e n )(p -T o l)(B r) 2 ]

-4

[C u (b e n )(p -T o l)(C l) 2 ]

-6

0

2

4

6

k (Å )

Fig. 2: χ (k) versus k curves for the copper complexes

450 400

[C u (b e n )(p -T o l)(N O 3 ) 2 ] 350

[C u (b e n )(p -T o l)(B r) 2 ]

300

E(eV)

250 200 150

[C u (b e n )(p -T o l)(C H 3 C O O ) 2 ] 100

[C u (b e n )(p -T o l)(C l) 2 ]

50 0 2

4

6

8

10

12

Q

Fig. 3: Q versus E curves for the copper complexes

[ C u ( b e n ) ( p - T o l) ( C l) 2 ]

8

[ C u ( b e n ) ( p - T o l) ( B r ) 2 ] 6

[ C u ( b e n ) ( p - T o l) ( C H 3 C O O ) 2 ] 4

n

[ C u ( b e n ) ( p - T o l) ( N O 3 ) 2 ] 2

0

-2 0

2

4

6

8

10

k (Å )

Fig. 4: n versus k curves for the copper complexes

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Extended Fine Structure of the X-ray K-Absorption Discontinuity in Some Copper(II) Mixed Ligand Complexes of Benz Aldehyde (IJIRST/ Volume 3 / Issue 12/ 017)

0 .8

0 .7

0 .6

-2

chi(R)(Å )

0 .5

0 .4

0 .3

[C u (b e n )(p -T o l)(C H 3 C O O ) 2 ]

0 .2

[C u (b e n )(p -T o l)(B r) 2 ]

0 .1

[C u (b e n )(p -T o l)(N O 3 ) 2 ] 0 .0

[C u (b e n )(p -T o l)(C l) 2 ] 0

2

4

6

8

10

R (Å )

Fig. 5: Magnitude of Fourier transform of the χ(k) versus k curve for Cu(II) complexes Table – 3 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 R1 ( Å) Lytle’s Method RS ( Å) LSS method R1 - α1( Å) Fourier transform R ( Å) [Cu(ben)(p-Tol) (NO3)2] 2.15 1.17 1.61 1.66 [Cu(ben)(p-Tol)(Cl)2] 2.24 1.75 1.61 1.63 [Cu(ben)(p-Tol)(Br) 2] 2.11 1.47 1.36 1.18 [Cu(ben)(p-Tol) (CH3COO)2] 2.28 1.71 1.57 1.51

IV. CONCLUSIONS 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, are in good agreement with each other.

ACKNOWLEDGEMENTS 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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