World Applied Programming, Vol (2), Issue (6), June 2012.

389-393
ISSN: 2222-2510
2011 WAP journal. www.waprogramming.com

Synthesis, Characterization and Electrochemical Study of

La(III) Complex With Polypyrydyl Ligands
Mohammad Hakimi *

Alireza Rezvani

Hamideh Saravani

Aazam Narooie

Chemistry Department
Payame Noor University
19395-4697 Tehran

Department of Chemistry,
Faculty of Science,
University of Sistan &
Balouchestan, I.R.I ran

Department of Chemistry,
Faculty of Science,
University of Sistan &
Balouchestan, I.R.I ran

Chemistry Department
Payame Noor University
19395-4697 Tehran

Abstract: One group of novel complexes,{[La(bipy)]2.(phen-dione)(dca)}(NO3)5.6(H2O) have been

synthesized. Dark green crystals of {[La(bipy)]2.(phen-dione)(dca)}(NO3)5.6(H2O) were formed into an
acetonitrile solution. This complex contained water molecule (the amounts of which were determined by
CHN analysis). The complex was characterized by elemntal analysis, FT-IR, electronic absorption
spectroscopies, 1H-NMR and Cyclic voltammetry. The electrchemical properties of the complex were studied
by Cyclic voltammetry. Cyclic voltammetry study of this complex, showed three pairs of peaks in the
negative region and one pairs of peaks in the positive region which were assigned to the consecutive
reduction of phen-dione and bipy ligands and other quasi-reversible reduction couple is assigned to the
reduction of La(III) centers.
Key word: La()complex, Dicyanamide, Phen-dione, 2,2'-bipyridin.
I.

INTRODUCTION

Paramagnetic centers have been found to be able to interact through extended bridging ligands, even if these centers
are relatively far away from each other. A number of molecule- based magnetic materials have been found to consist
of paramagnetic metal ions and organic species [1,2].
Dicyanamide (dca) bridged polynuclear transition metal complexes constitute a hot subject of research, metal
dicyanamide compounds are of great interest due to the variety of abserved topologies, this bing related to the
versatility of dca as a ligand, and its potential application in functional materials. Surprisingly, most of the reported
dca bridged transition metal complexes have focused on low-oxidation state systems [3].
On the other hand, dicyanamide is a versatile ligand with three nitrogen donor atoms; it may act as a uni-, bi-, and
tridentate ligand [1]. (dca) has been shown to be a versatile ligand and may coordinate to metal ions as a terminal
ligand through a nitrile or amide nitrogen.
Complexes of 1,10-Phenanthroline-5,6-dione (phen-dione) ligand have been extensively studied. Phen-dione is a
well- known NN chelating agent with a rigid planar structure.
The phen-dione complexes, similar to other polypyridine complexes, exhibit optical and electrochemical properties,
metal-to-ligand charge transfer (MLCT) in the visible light region, reversible reduction and oxidation, and fairly
intense luminescence [4,5]. Regarding these properties, however, slight differences exist between phen-dione
complexes and bipyridine complexes. Phen-dione ligand plays important roles as molecular scaffolding for
supramolecular assemblies, building block for the synthesis of metallo-denderimers and thin films of luminescent
complexes [5-7]. Metal complexes of the type [M(LL)3]n+, where LL is either phen-dione or 1,10-Phenanthroline
ligand, are particularly attractive species for developing new diagnostic and therapeutic agents that can recognize and
cleave DNA [5,8]. Also we reported complexes is containing (bipy) ligands that derived from a bischelating ligand.
We report here the syntheses of one novel complexes containing rare earth metal {[La(bipy)]2.(phendione)(dca)}(NO3)5.6(H2O) ,(Phen-dione)= 1,10-Phenanthroline-5,6-dione,
(dca)= Dicyanamide, (bipy)= 2,2'bipyridin.

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II.

EXPRIMENTAL

Materials and Measurements

All salts used in the preparation of complex were purchased from Aldrich Company, (bipy) was purchased from Fluka
Company, all solvents used were purchased from Merck Company and 1,10-Phenanthroline-5,6-dione was synthesized
according to the literature procedure [5,9-11].
Elemental analyses (C,H,N) were determined on an Eager 300 Summarize analyzer.
FT-IR spectra were recorded as KBr pellets on a JASCO 460 FT-IR spectrophotometer and electronic spectra on a
JASCO 7850 spectrophotometer [1]. 1H-NMR spectra were recorded on a Bruker DRX-500 MHZ, Avance
spectrometer at ambient temperature in H2O. Cyclic voltammograms were recorded by using a SAMA500
electroanalyzer system.

Synthesis of {[La(bipy)]2.(phen-dione)(dca)}(NO3)5.6(H2 O)
La(NO3)3.6H2O (2mmol, 0.866mg) dissolved in 20mL (CH3CN) Solvent. To a solution of La(NO3)3 in (CH3CN) was
added 1,10-phenanthroline-5,6-dione (0.210mg, 1mmol) dissolved in 20mL (CH3CN).
After 1h stiring, A solution of sodium Dicyanamide (1mmol ,0.089mg) dissolved in 15cc (CH3CN) and H2O was
added slowly with stirring. After stirring at 180C for 24h, a solution of 2,2-bipyridin (2mmol , 0.312mg) dissolved
in 20cc (CH3CN) was added slowly to the refluxing mixture, and refluxing was continued for 24h. After stirring at
180C for 24h the resulting solution was filtered to remove any undissolved materials. A dark green crystalline
product separated after several days. The product (58.8% yield) was obtained according to the workup procedure
outlined in this method.
mp: 167C (dec). Calcd for C25H17LaN2O7 : C, 32.6; H, 2.74; N, 15.66 Found: C, 32.05; H, 2.58; N, 16.27. FT-IR
(KBr disk, cm-1): (OH) 3402.2(w); s(CN)+as(CN) 2283.6; s(CN) 2160.1(s); (C=O) 1689.5(m); (C=N)
1573.8(m); (C-N) 1303.8(s); s(C-N) 925.8(w). UV-vis (H2O) 211nm (4.29), 236nm (2.18), 255nm (2.21). 1H-NMR(
H2O): 8.74 -7.36 (11H,aromatic). Cyclic voltammetry study of this complex in DMF, showed three pairs of peaks in
the negative region and one pairs of peaks in the positive region, that they are at E1/2 = -0.13, -0.72, -2.047 and 1.395V.
III.

RESULTS AND DISCUSSION

The coordination modes of dca ligands can be classified as two types of bridging and terminal ligands [1].
The Ln-N(O) bond lengths become shorter with the increase of the atom number of Ln due to the lantanide contraction
[1].
The neutrality requirement suggests a formal oxidation state of +3 for lanthanide cations [1].
Due to the poor solubility of La and phen-dione in common organic solvents such as acetonitrile, the Nitrate salt of the
complex was replaced by dca and bipy salts [5].
The complex {[La(bipy)]2.(phen-dione)(dca)}(NO3)5.6(H2O) is air-stable and can be readily recrystallized.
The Elemental analysis of the complex was consistent with C25H17LaN2O7 Formula.
The phen-dione ligands are coordinated via the C=O and N moieties to the metal centers [5,6].
The wide and strong absorption bands at 3402.2cm-1 related to the OH groups of water molecules [12]. The absorption
band at 2283.6cm-1 related to the s(CN)+as(CN) group of the Sodium dicyanamide ligand [13].
The strong absorption band at 2160.1cm-1 was assigned to s(CN) of the Sodium dicyanamide ligand [13].

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The IR spectrum of the free phen-dione showed a sharp band at 1675cm-1, which associated with the stretching
frequency of the C=O band of the ligand. The observed band did not shift significantly in comparison with the
corresponding complexes. This was reasonable since the C=O moieties were far from the coordination site of the
ligand with the metal ion [5,9,14,15]. The IR spectrum of the complex showed a band around 1689.5cm-1, which was
assigned to the (C=O) band of an O-quinoid group of the phen-dione ligand. In general, the carbonyl stretching
frequency was relatively insensitive to change in the metal center, a reflection of the fact that the effect of the metal
center and its coordination environment on the carbonyl stretch was a secondary one[5]. The medium absorption band
at 1573cm-1 was assigned to (C=N) of the 2,2'-bipyridin ligand[16-17].
The strong absorption band at 1303.8cm-1 was assigned to (C-N) of the amine groups [18]. The weak absorption band
at 925.8cm-1 was assigned to s(C-N) of the Sodium dicyanamide ligand [13]. The electronic spectrum of the complex
that was recorded in H2O solution (Fig.1). The electronic absorption spectra of complex is dominated by high energy
ligand-centered ( *) transitions (IL) in the range 211, 236 and 255 nm [5,14,19-21].
The solvent dependency of(n *) energy on the solvent polarity, which is a well-known phenomenon, was the
reason behind such an assignment [5,21,22].
1

H-NMR spectroscopy of complex conrmed the presence of aromatic parts ( Fig.2).

The 1H-NMR spectra showed signals in 7-8 ppm range that observed aromatic parts of bipy and phen-dione ligands in
the 7-8 ppm.
Cyclic voltammetry was performed in an DMFsolution of {[La(bipy)]2.(phen-dione) (dca)}(NO3)5.6(H2O) with 0.1 M
TBAH as a supporting electrolyte at scan rate 0.1 - 0.5 Mv. S-1 (Fig.3). The formal potentials for the processes are 0.45 and -1.25 V, and they represent formation of the ion radical and dianion of the free phen-dione ligand [5,23,24]
that in this voltammogram, two quasi-reversible reduction couples at E1/2= -0.13and E1/2= -0.72V are assigned to the
reduction of phen-dione ligand. In comparison with free phen-dione, the reduction couples shift to more positive
potentials due to the coordination of phen-dione ligand to the La(III) center [5]. One quasi-reversible reduction couple
at E1/2= -2.047V is assigned to the reduction of bipy ligand [16,17] and other quasi-reversible reduction couple at
E1/2 =1.395V is assigned to the reduction of La(III) center.

-5

Fig.1. UV-Vis absorption spectra of {[La(bipy)]2.(phen-dione)(dca)}(NO3)5.6(H2O) in H2O (10 M)

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Fig.2. H NMR spectra of {[La(bipy)]2.(phen-dione)(dca)}(NO3)5.6(H2O) in D2O.

Fig. 3. Cyclic voltammogram of {[La(bipy)]2.(phen-dione)(dca)}(NO3) 5.6(H2O) in DMF at scan rates of 0.1 - 0.5 mV s
1

; 0.1 M TBAH as a supporting electrolyte.

ACKNOWLEDGMENTS
We gratefully acknowledge financial supported by Payame Noor University, and University of Sistan and
Baluchestan.
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Mohammad Hakimi received the B. Sc degree in chemistry from the Ferdowsi University of Mashhad, Iran in
1993 and the Ph. D. degree in inorganic chemistry from Ferdowsi University of Mashhad in 2003. He has
published over 40 peer-reviewed journal papers and contributed to more than 30 conference papers and
presentations. He was collaborated in chemistry group of Newcastel University during 2008. His research
activities include synthesis of Co, Cu, Ag, Au and Cd complexes in low oxidation, metal triazole and triazine
complexes, Amino alcohols complexes, mixed ligand complexes, nano polyoxometales & theirs catalysis and
macrocyclic chemistry. He has published three books in advance inorganic chemistry and inorganic chemistry
issue one and two during 2007 to 2011.

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