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Jamonline / 2(3); 2012 / 262272 Research Article

Chaudhary R.G et al

Journal of Atoms and Molecules


An International Online Journal
ISSN 2277 1247

PREPARATION, CONDUCTIVITY AND MORPHOLOGY BEHAVIOR OF BIS (BIDENTATE) LIGAND AND ITS CHELATE POLYMERS Ratiram G. Chaudhary1*, Harjeet D. Juneja2, Mangesh P. Gharpure2
2

Department of Chemistry, Seth Kesarimal Porwal College Kamptee, Maharashtra, India Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur-440 033, Maharashtra, India Revised on: 06-06-2012 Accepted on: 12062012

Received on: 30-05-2012 Abstract:

The present paper describes three chelate polymers of transition metals were synthesized by interaction between suberoyl bis (paramethoxyphenylcarbamide) with metal acetate using dimethylformamide as solvent. The newly synthesized chelate polymers were found colored and insoluble in all common organic solvents. The resulting polymers were characterized by elemental analysis, Fourier Transform Infrared Spectrophotometer (FTIR), X-ray diffractrometric and Thermogravimetric Analysis (TGA). The half decomposition temperature and lattice water of polymers were determined by thermogravimetric analysis. On the basis of above studies, the chelate polymers were found to have tetrahedral geometry. Furthermore, solid state conductivity of all chelate polymers has been measured in compressed pellet form over 311 K and found conductivity in range 6.15 10-10 1.8 10-5 cm-1 which indicates the semiconductor nature. The crystalline

and amorphous natures of metal chelate polymers were determined by X-RD. SEM studies determine surface morphology of polymers. SEM images of these chelate compounds were shown at higher magnification and data reveal that, particle sizes of chelate compounds were found to be micro level. This technique was noteworthy helpful to identify the difference in morphology of chelating ligand and their chelate polymers. Key Words: Chelate polymers, TGA analysis, Stable chelating agent, Bis (bidentate) ligand, SEM, XRD and electrical conductivity * Corresponding author Ratiram G. Chaudhary, Email: chaudhary_rati@yahoo.com Tel: +91 9860032754 All rights reserved 2011 Introduction: The synthesis of high molecular weight, highly aromatic metal chelate polymers has

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Jamonline / 2(3); 2012 / 262272 been a long- standing goal of chemist and these would be expected to have high degree of thermal and chemical inertness. Many chelate compounds have considerable value in concentration, separation, extraction of metal ions and several metal-chelate polymers are widely used in medical sciences (Yang et. al. 2004; Roy et. al. 2003 ) conducting materials, catalysts, activators and proteins (Naka et. al. 2002; Annunziata et. al. 2000). Furthermore study of high polymers with inorganic elements in their back bone or as pendent group, offer a for new area with broad and

Chaudhary R.G et al fungicide (Minoru and.Thoshio, 1962) and bind with toxins, viruses and bacteria (Dhal et al., 2005) The demands for new materials with practical applications have been

promoted research in design and synthesis of metal chelate compounds, on accounts of its various applications in biological processes (Wright et al., 2004; Sibert et al., 2002; Bencini et al., 2003; Valli et al., 2002) such as photosynthesis and dioxygen transport

(Dasivala et al., 1991), catalytic properties (Carburet et al., 2002) and surface coating (Paine et al., 1994). The work herein reported is concern with preparation of thermal-responsive metal-

opportunity

material

scientists

technologists looking for new classes of compounds that are attracting attention as high technology materials, biomedical

chelating polymers of SUBPMPC with Zinc (II), Cadmium (II) and Mercury (II) in dimethylformamide medium. Because of good thermal stability of chelating polymer, one of the most important applications is these can be used as high thermal stable materials and bidentate imides ligand can be used as antibacterial resistance compound. Experimental: Materials Zinc(II), cadmium(II) and mercury(II) acetate from Merck were used without purification. All solvents and chemicals used for the synthesis were of analytical reagent grade. The solvents were double distilled before used Physical measurements Infrared spectra of the bis-ligand and its metal chelate polymers were recorded on

polymers and electrical conductors (Rahimi, 2004). Such inorganic elements zinc and bulky organic moieties thiolate gives zinc thiolate reactivity, such as cysteine Salkylation, plays significant role in the function of proteins such as cobalamin independent and dependent methionine,

synthase and farnesyl transferase (Almaraz et al., 2009). However, various zinc chelate seen to be good substitutes for zinc oxide as activators, sulphur vulcanization of NBR rubber, without dentrimental effect on the cross linking process and physical properties of the obtained vulcanizates (Przybyzewska et al., 2009). The various chelate compounds of transition metals are also performed

interesting role in anticorrosion primer,

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Jamonline / 2(3); 2012 / 262272 Shimandzu FTIR-8101A instruments. The 1H NMR spectra of ligand were carried out on Bruker-Avance II400 spectrophotometer

Chaudhary R.G et al (bidentate) ligand (SUBPMPC) i.e. suberoyl bis (paramethoxyphenylcarbamide) was given in previous publication (Chaudhary et al., 2012). Synthesis of chelate polymers The solution of metal acetate (0.01 M) in DMF (20 mL) was added to a solution of SUBPMPC (0.01M) in DMF (20 mL). The mixtures was stirred and refluxed at 150 0C for 20-24 h. Obtained metal chelate

using DMSO and TMS as internal standard. Elemental analyses were carried out using a Perking-Elmer CHN/O elemental analyzer model 2400. Thermogramometric analyses reports were obtained on Perkin Elmer SII, Diamond TG/DTA.
0

Thermogramometric

analyses were carried out in the range of room temperature to 800 C and water of

crystallization was lost in the temperature range 100 0C-145 0C. X-ray diffraction were recorded on PAN Analytical Diffractometer. Synthesis of bis (bidentate) ligand Acid dichloride was synthesized by standard procedure (Ukey et al., 2005). The study of preparation and characterization of bis X pert PRO

compounds were filtered and washed with hot DMF, DMSO and then dried in oven. All chelate polymers were found to be insoluble in almost all common organic solvents. The physico-chemical properties of bis (bidentate) ligand and metal chelate polymers have been tabulated in Table 1, while the elemental analyses data are given in Table 2.

DMF+ Alcohol, M(CH3 COO)2 + SUBPMPC Reflux, 20-24 h in an oil bath Ligand Metal Acetate

150 0C

[M (SUBPMPC)] xH2O Chelate polymers

where M= Zn(II), Cd(II) and Hg(II)

Table1. Physico-chemical data of SUBPMPC and its metal chelate polymers Chelate polymers/Ligand M.P.0C SUBPMPC 250 Color Empirical Formula Molecular Wt. Yield %

White

C24H30N4O6

470.58

81.12

{[Zn(II)SUBPMPC]H2O}n Off white 408

C24H30N4O7Zn

536.58

64.45

{[Cd(II)SUBPMPC]2H2O}n Pale yellow C24H32N4O8Cd 436 {[Hg(II)SUBPMPC]2H2O}n Light green C24H32N4O8Hg 389

614.58

65.49

693.58

69.31

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Jamonline / 2(3); 2012 / 262272 Table 2. Elemental analyses of SUBPMPC and its metal chelate polymers Polymers %Carbon Obs. Calc Cal. 61.1 61.2 53.7 46.8 41.5 %Hydrogen Obs. Calc. 6.2 5.39 5.11 4.55 6.3 5.6 5.2 4.6

Chaudhary R.G et al

%Nitrogen Obs. Calc 12.7 10.21 8.95 8. 10 12.6 10.4 9.1 8.0

%Metal Obs. -12.1 18.2 28.8

SUBPMPC --

{[Zn(II)SUBPMPC]H2O}n 53.9 12.2 {[Cd(II)SUBPMPC]2H2O}n 46.5 18.3 {[Hg(II)SUBMPC]2H2O}n 41.6 28.9

Results and discussion Suberoyl bis paramethoxyphenylcarbamide is basically having high melting point and basic in nature. A bis (bidentate) ligand forms chelate polymers via nitrogen and oxygen donor atoms. Metal chelate polymers were synthesized in 1:1 stoichiometry ratio by metal acetate and bis-ligand in
M
NH

OCH3

C O N C
O

(CH2)m

O C N C O
NH

H2 O

dimethylformamide medium. Newly resulting chelate polymers were found to be air-stable, non-hygroscopic, colored solid, semi-

crystalline, thermally stable and insoluble in almost all common organic solvents. The presences of water crystallization were

OCH3

determined on the basis of elemental analysis, TGA and FTIR data. On the basis of elemental analysis, FTIR, 1H NMR, thermal and X-ray diffraction studies, proposed structure of chelate polymers have been shown in Fig. 1.

Fig. 1. Proposed structure of chelate polymers, where m= 6 (SUBPMPC) and M= Zn (II), Cd (II) and Hg (II) and H2O = lattice of water

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Jamonline / 2(3); 2012 / 262272 Infrared spectral studies The desire spectral features of prepared bisligands were assigned and their infrared frequencies have shown in Fig. 2a-c. The infrared spectra provide valuable information regarding the nature of functional group of bis-ligand attached to transition metal ions and as well as occurrence of new bands in the region 476-692 cm1, which were absent in the free ligand; these can be attributed to metal-oxygen and metal-nitrogen bonds,

Chaudhary R.G et al and such corresponding bands is also seen in chelate polymers. In case of ligand band observed at 1691 cm-1 may be due to

stretching mode, however it disappears and new bands are observed around at 13551490 cm-1 in polymer which clearly

indicates that the presence of C=O bond disappear due to the formation of C=N bond as result of enolisation. This has been supported by appearance of C-O band around 1045-1099 cm-1 in case of chelate polymers (Nakamuto and Makurthy, 1968). The -OH bond disappears in chelate polymers

respectively. In present investigation, of SUBPMPC infrared spectrum exhibits sharp band at 3245 cm-1 which may be assigned to stretching 3350 cm-1 hydrogen vibration of the N-H group

indicating the formation of O-M bond. This suggests the formation of chelate ring through oxygen of bis (bidentate) ligand with release of proton of O-H group. M-O at 500-600 cm-1 bond

(Dyer, 1978). The sharp peak appeared at because bonding of intermolecular and compound

formation is confirmed by the newly weak band appeared while

containing secondary amine, which shows single weak band in range at 3350-3310 cm-1 region (Silverstein, 1981). 1691-1695 cm-1 region The bis

presence of weak band in range 425-581 cm-1 may presence be due of broad to M-N band bond. The observed in

(bidentate) ligand shows sharp band at range which may be

coordination polymers due to free H-OH stretching vibration of lattice water (Maurya et al., 1980) in range at 3300-3450 cm-1.

assigned to stretching frequency of >C=O group and also a sharp band observed at 1228 cm-1 assign to the C-N frequency (Shrivastava and Kalam, 2006). The sharp band appeared at range 2932-2939 cm-1 may be due to aliphatic CH2 group frequency which is also observed in metal polymers. A band appeared at1601 cm-1 which is due to C=C stretching vibration in aromatic ring (Seal, 1996) as well as band appeared at1560 cm-1 may be due to the presence of phenyl group frequency All rights reserved 2011

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Jamonline / 2(3); 2012 / 262272

Chaudhary R.G et al

Fig. 2. Infrared spectra of (A) ligand (B) Cd(II) and Hg(II) chelate polymer

X-ray Diffraction Studies In present course of studies difractogram of metal chelate polymers have been recorded, interpreted and reported. On the basis of Xray analyses, it has been observed that natures of chelate polymers were orthorhombic. All these reflections are indexed for h k l values using method reported in literature (Pimental et al. 2005; Davies et al., 2004). Well defined sharp peaks found in diffractrogram of {[Zn (II) SUBPMPC] H2O}n {[Cd(II) SUBPMPC] 2H2O}n whereas weak peaks in{[Hg(II) SUBPMPC]2H2O}n. Therefore, its concluded All rights reserved 2011

that

metal

chelate

polymer

{[Hg (II) SUBPMPC] 2H2O}n amorphous in nature, while {[Zn(II) SUBPMPC] H2O} and {[Cd(II) SUBPMPC] 2H2O}n are semi crystalline. Reflection was determined with the help of Braggs equation i.e. 2d sin = n. These polymers were found to be

orthorhombic in nature crystal represented by a: 1: c and the values of sin and 2 for each peak have been determined with the help of cell parameters and corresponding h k l values.

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Jamonline / 2(3); 2012 / 262272 Conductivity The molar conductivities and PH of 10-3 solution of SUBPMPC in DMF medium were measured at temperature 25 2 0C. By using the relation m = K/ C, the molar conductance of amide ligand can be measured and where C is concentration of amide ligand solution. The molar conductance and PH measurements were carried out at different dilution. The molar conductance at 0.0347 mol g-1 (78
-1 -1 -1

Chaudhary R.G et al it may be considers as coordination water. The TGA curve for Zn(II), Cd(II) and Hg(II) chelate polymers were shown (Fig. 3a-c) at heating rate 10 0C min-1. The decomposition of chelate polymers were may be divided into two stages. The first stage may be due to the weight loss of lattice water and second stage was due weight loss of organic moieties. In thermal study of SUB4-MPC-Zn weight loss was observed up to 140 0C may be due to removal of lattice water, as well as it was confirmed by CHN analyses and infrared spectrum at 3372 cm-1. At 120 0C -140 0C correspond to 3.28 % weight loss due to of one molecule of lattice water. After 1400 C2500C no loss of weight was observed, it may be due to the absence of coordination water, therefore it supporting tetrahedral geometry for this chelate polymer. The gradual loss of mass observed in the range of 260 0C-522 0C which was attributed to the degradation of organic part of ligand. The rate of

Mol-1 cm2) shows good conductivity while 0.0119 (128 g-1 (198 Mol-1 cm2 ) and 0.0244 mol Mol-1 cm2) shows moderate

conductivity, hence it indicate the ionic nature of ligand. The electrical conductivities, measured at in compressed pallet form over 311 K of three chelate polymers. These were found an average range of 6.15 10-10 1.8 10-5 cm-1 which indicate the semiconductor

in nature. The low conductivities were shown by Hg(II) polymer, therefore it may consider as poor semi conducting in nature and high order of conductivity was shown by Cd(II) and Zn(II) complexes, hence they acting as moderate semi conducting nature. Thermal studies In general water of hydration may be considered either coordinated water or lattice water. According to Singh et al. (Singh et al., 1982) and (Nikolaev et al., 1969)
0 0

degradation was steady till this stage, and slow down without showing any steep change. This happen due to the decrease in the coefficient of thermal conduction. This type of behaviour is characteristics of such types of compound, after that no weight loss is observed, indicating the formation of stable species may decomposition be metal oxide and half of chelate

if

temperature

water eliminated in range of 120 C-150 C can be considered as lattice water and if water eliminated in range of 150 C-250 C
0 0

polymer was found to be 408 0C. Similarly, the thermogram of Cd(II) and Hg (II) chelate polymer, shows that loss of mass up to 155

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Jamonline / 2(3); 2012 / 262272


0

Chaudhary R.G et al which may be due to decomposition of organic species and then it forms stable

C and it correspond to 5.78% and 5.18%

weight loss due two molecule of lattice water respectively. Then weight loss stop up to 230
0

metal oxide. Thus thermal studies of chelate polymers favour tetrahedral geometry. The half decomposition temperatures of Cd (II) and Hg (II) chelate polymer were found to be 436 0C and 389 0C respectively.

C may be

due to absence of water of

coordination. The presences of lattice water were confirmed by CHN analyses and band at 3353-3378 cm-1 in infrared spectra. Thus the weight loss start from 230 0C to 510 0C,

Fig. 3. TGA curve of a. Zn(II), b. Cd(II) and c. Hg(II) chelate polymer at heating rate 10 0C min-1

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Jamonline / 2(3); 2012 / 262272


SEM Analysis SEM studies determine surface morphology of chelate polymers. SEM images of these metal chelate polymers (Fig. 4a-c) were recorded at energy of 20 kV with magnification X 1, 500 forchelate polymers. This technique was

Chaudhary R.G et al
was found that, the morphology of individual chelate compound significantly different from other chelate polymers at magnification X 1, 500. Though the morphologies of all chelate polymers were found distinct, yet it was synthesized from a particular ligand. The surface morphology of Zn-chelate polymer (Fig. 4a) is totally different from ligand. The Zn(II) chelate polymer shows rose flower and beads shape structure. The numbers of beads were appeared in various dimensions.

noteworthy helpful to identify the difference in morphology of chelating ligand and their chelate polymers. The micrograph of ligand is totally different from chelate polymers; hence it is the conspicuous of formation of new product. Also it

Fig. 4. SEM images of a. Zn(II), b. Cd(II) and c. Hg(II) chelate polymer

The beads are seen like globule and flower type. The huge mass appeared due to the

Scanning electron microscopy image of Hg(II) polymer (Fig. 4c) observed like cotton threads spread over the surface, hence it indicates the polymerization of compound. Scanning electron microscopy image of three chelate polymers were found noteworthy www.jamonline.in 270

collection of number of beads. The Cd(II) chelate polymers (Fig. 4b) found broken leaf shape structure and spread randomly. Some structure where seen like small beads shape. All rights reserved 2011

Jamonline / 2(3); 2012 / 262272 distinct from each other. SEM images chelate polymers were reveals that the particle sizes found to be micro level size. Conclusion Bis (bidentate) ligand and chelate polymers were found distinct colored and insoluble in common organic solvents. By performing study of TG analyses the chelate polymers were found thermally stable. The presence of lattice water were determined on the basis of infrared, thermal studies and CHN 7. 6. 5. 4.

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tetrahedral geometry. Acknowledgements Authors heartily acknowledged to University Grants Commission, New Delhi for awarding Rajiv Gandhi National Fellowship for

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