Microsoft Word - 169-186 169 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Synthesis, Structural and Biological Efficiency Studies of New Azo Ligands and Their complxes with Zn(II), Cd(II) and Hg(II) Metal ion Alyaa K. Abass Dept.of Chemistry/ College of Science / University of Baghdad Received in: 24/May/2015, Accepted in: 23/June/2015 Abstract The formation of Zn(II), Cd(II) and Hg(II) complexes was studied with two new hetrocyclic azo ligands 2-[4-(1-sulfonaphthalene)azo]-L-Histidine (L1) and 2-[7-(1-hydroxy- 3-sulfonaphthalene)azo]-L-Histidine (L2) derived from coupling reaction of diazonium salt of naphthionic acid and 7-amino-1-naphthol-5-sulfonic acid with L-Histidine in an alkaline ethanolic solution. The structural features of all new compounds have been characterized from their elemental analyses, metal content, magnetic moment measurement, molar conductance & FT-IR, UV-Vis. and 1HNMR spectral studies. Furthermore,the composition of complexes have been studied following the mole ratio method after fixing the optimum condition (pH and concentration).Beer’s law was obeyed over a concentration range (610-5 - 810-5M). All data showed that the complexes with (1:2) (M:L) metal to ligand, may be formulated as [M(L)2Cl2] and octahedral geometry, in which the ligands (L1 and L2) act as N,N-bidentate chelating agents, coordinated through the azo nitrogen near naphthyl moiety and heterocyclic nitrogen in L-Histidine. The stability constant () and Gibbs free energy (G) of the complexes have also been studied. Biological efficiency of ligands and their complexes were tested aginst Eschericha coli and Staphylococcus aureus. Keywords: L-Histidine, Azo lignads, structural studies, biological efficiency. 170 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Theoretical Scientists found that some naphthalen derivatives have been embodied as new range of active antimicrobials effective against a wide range of human phathogens [1] and thus considered medicinally important part of antibiotic drugs such as nafacillin, naftifine, tolnaftate, etc. which play vital role in the control of microbial infection [2]. The synthesis and development of biologically active compounds have received much attention in the literature [3], and prompting the medicinal chemist have always tried to prepare drug of maximum therapeutic application and minimum toxicity [4].On the other hand the literature survey on synthetic naphthyl azo heterocyclic compounds containing active azo imine moiety (-N=N-C=N-), showed that they act as N,N-donor atoms and -acidic ligand [5] with higher electron negativity of C and N [6]. Moreover they have been studied extensively in which the heterocyclic atoms at formally involved in the coordination to a positively charged metal centre might confirm the reactions of nucleophiles with the ligand and thus formed a stable five or six-membered ring assigned to the presence of π*-molecular azo centered [7], therefore activites of metal complexes differ from those of either the free ligands or metal ions [8]. This type of compounds has been used in a number of biological reactions such as inhibition of RNA, DNA and protein preparation, nitrogen establishing, antifungus and anticancer agent [9]. Furthermore azo compounds play an important role in many applications that involve textile dyestuff industry [10] additives [11], cosmetic [12], organic synthesis [13], analytical [14], and non-linear optics [15] as well as photoelectronics [16] especially in optical information storage [15]. All these applications based on high intensity absorption bands in the UV-Vis region which include at least a conjugated chromophore azo (-N=N-) moiety in combination with one or more aromatic heterocyclic ring [16]. In spite of having good thermal stability as well as more light stable, weather fastness and impedance to solvents and water [17]. However this type of compounds is less reported, here in this paper the preparation, characterization and antibacterial efficiency of two new ligands, 2-[4-(1- sulfonaphthalene)azo]-L-Histidine (L1) and 2-[7-(1-hydroxy-3-sulfonaphthalene)azo]-L- Histidine (L2) and their metal chelate complexes with [Zn(II), Cd(II) and Hg(II)] ions are investigated Experimental Materials and Instruments All reagents and solvents are of highest purity and used as obtained from the manufactures. Microelemental analysis (C.H.N.S) was gained on a (Euroveetor EA 3000A Elemental Analyser) in Al-al-Bayt University- Jordan. UV-Vis. Spectra were performed in ethanol on a (Shimadzu UV-160A) ultra violet-visible spectrophotometer. IR-spectra were recorded on a (Shimadzu FTIR-8400s Fourier Transform Infrared) spectrophotometer (200-4000) cm-1 using CsI discs. The 1HNMR spectra were gained on a (Jeol Ex270 MHz, Brucker-400MHz) University of Al-Al-Bayt-Jordan using DMSO as a solvent and (TMS) as a references. Conductivities were determined for (10-4M) of complexes in ethanol and DMSO at 25C using (HANNA instruments / Conductivity Tester). pH measurement were performed using (HANNA instruments pH Tester / Pocket pH Tester). Melting points have been gained by using (Stuart Melting Point Apparatus). 171 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Synthesis of Naphthyl Azo Ligands (L1 and L2) The ligands (L1 and L2) were prepared as in literature [18] by coupling reaction of L- Histidene with the proper diazonium salt, as shown in Scheme (1) below: A NH2 B A N B NHSO4 A N B N N N CH2CHCOOH NH2 NaNO2 H2SO4 [conc.] 0oC L-Histidine (NaOH) L1 = [A = SO3H ; B = H]; 2-[4-(1-Sulfonaphthalene)azo]-L-Histidine L2 = [A = SO3H ; B = OH]; 2-[7-(1-hydroxy-3-Sulfonaphthalene)azo]-L-Histidine A concentrated sulphuric acid (5 ml) was added to precooled aqueous solution of (0.1 mole, 6.9 gm) sodium nitrite till brown fumes were evolved. Then the resulting solution was added dropwise at (0C) to (0.01 mole; 2.23 gm and 2.40 gm) of ethanolic solution of the proper amine (naphthionic acid and 7-amino-1-naphthol-5-sulfonic acid respectively. The diazonium sulphate solution was added dropwise with stirring to (0.01 mole, 1.55 gm) an alkaline solution of L-Histidine cooled below (0C). The resulting mixture was stirred for (2 hr.) in an ice bath. The product is left in the refrigerator for (24 hr). And then the colored products were filtered, washed several times with (1:1) EtOH:H2O, and dried in vacuum desicator. (M.P. = 260 and 272C for L1 and L2 respectively). Synthesis of Complexes The complexes were prepared by adding gradually with stirring hot ethanolic solution of (2mmole) of ligands to stoichiometric amount of (1:2) (M:L) mole ratio (1mmole) of metal chlorides of [Zn(II), Cd(II) and Hg(II)] were dissolved in the buffer solution at optimum pH. The resultant mixture was heated at (60C) with stirring for (2 hr), then left to cool to room temperature . The colored precipitates were filtered, washed and dried in vacuum desicator.The expected stereochemical structure of the complex is shown in Scheme (2). M Cl Cl A N B N N N R A N B N NN R CH2CHCOOH NH2 R = M = Zn(II) , Cd(II) and Hg(II) L1 = [A = SO3H ; B = H] L2 = [A = SO3H ; B = OH] 172 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Buffer Solution (0.01M, 0.771 gm) of ammonium acetate was dissolved in one liter of doubly deionized water. For adjusted pH range (4-10) was used acetic acid or ammonia solution. Standard Solution A series of standard solutions of metal chlorides of [Zn(II), Cd(II) and Hg(II)] were prepared in different concentration (10-6-10-3 M) at pH range (4-10). At the same time a series of ethanolic solutions of ligands (L1 and L2) within the range of concentrations (10-6-10-3 M) were also prepared. Study of Biological Efficiency The agar-well diffusion method [19] was used to screen the antibacterial activity. The in vitro antibacterial activity of the synthesized ligands (L1 and L2) and their prepared complexes in ethanol(10-4M) were tested against Gram-positive bacteria: Staphylococeus aureus and Gram-negative bacteria: Escherichia coli using nutrient agar medium. Then (0.1 ml) of test solution was added carefully in spot on the surface of inoculated solid media. The petridishes were incubated at (37C) for (24 hr). The inhibition zone formed by the compounds against the particular test bacterial strain were measured in diameters to evaluate the antibacterial activities of the prepared compounds. Results and Discussion A well established synthetic route to azo compounds is based on general procedure for the diazo-coupling reaction [18, 19]. Azo compounds are prepared by diazotization of hetrocyclic or aromatic primary amines and followed by coupling the diazonium salt to a nucleophile, like aromatic heterocyclic or substituted aromatic ring [20]. which at least azo moiety linked to sp2-hybridized carbon atoms [21], according to it, has been prepared the lignads (L1 and L2) as in Scheme (1). The elemental analysis data of the prepared (L1 and L2) and their complexes with [Zn(II), Cd(II) and Hg(II)] are in good convention with the calculated result from expected formula of each synthesized compounds Table(1). which indicates that diazo-coupling reaction between the diazotized aminonaphthalene and L- Histidine occurred in a (1:1) molar ratio. The lignads and their complexes are stable at room temperature, non hydroscopic and slightly soluble in water but soluble in most organic solvents. All the prepared complexes recorded high melting points (> 360C). Calibration Curve It was constructed as in the general procedure [22]. Several molar concentration (10- 6–10-3 M) of mixed aqueous-ethanolic of ligands and metal ions, only the concentration in the range (6-8×10-5M) obeyed Beer’s law and appeared perspicuous intense color.Best fit straight lines were obtained with correlation factor R>0.9991as shown in Figure.(1). Optimum Conditions To investigate the interaction between the prepared ligands and metal ions under study for the preparation of the complexes,the spectra of blending solutions for the ligands and metal ions to reach to optimum pH and concentration, as well as fixed wave length (max)were studies first .Then mole ratio metal to ligand (M:L) was appointed to prepare the complexes. Optimum concentration was chosen for complex solution based on which solution gives the highest absorbance at constant (max) at different pH. And results are described in Table (2). 173 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 The empirical results proved that the absorbance of all prepared complexes are maximum and constant in a buffer solution of ammonium acetate in the pH range (4-10).It was found that all prepared complexes had optimum performance at (pH = 7) as is shown in Figure (2). Absorption Spectra The reaction of the prepared ligands (L1 and L2) with metal ions under study at optimum conditions in solution were studied. The absorption spectra showed an absorption maximum (max) for ethanolic solution for (L1 and L2) at (387 and 375 nm) respectively, whereas the ethanolic-aqueous solution for their complexes are located at wave length range (429-518) for (L1) and (546-570 nm) for (L2). Hence a great red shift in the visible region was observed in the complexes solutions spectra when compared with the spectra of ethanolic solution of the free ligands which confirm the complex formation. Figure (3) shows a comparison between the spectra of L1 and [Zn(II)-L1] mixed solution. Stoichiometry of Complexes The composition of the prepared complexes performed in solution by mole ratio method at exact pH and concentration at certain wavelength of maximum absorption (max). The ratio was (1:2) metal ion to ligands at pH (7) Figure (4 and 5). The condition for the preparation of complexes are presented in Table [2]. All obtained results are in agreement with the values recorded for some naphthyl azo imidazole complexes [22]. Determination of Stability Constant and Gibbs Free Energy The successive stability constant () of the (1:2) metal:ligand complex can be calculated from the relationship [23]: m sm 23 A AA ; C4 1      Where: Am and As = the absorbance of the fully and partially formed chelating complex respectively at optimum pH and concentration at (max) of solution C = the molar concentration of the complex solution  = degree of dissociation The values of () and log  for prepared complexes are give in Table (2). The high values of ()refers to high stability of prepared complexes, which they follows the sequence,; [Hg(II) > Zn(II) > Cd(II)] for (L1) complexes while for (L2) complexes have been noticed the sequence [Cd(II) > Zn(II) > Hg(II)],that basis on the differences between stereochemical structures of the two ligands (L1 and L2) [24]. The thermodynamic parameters of Gibbs free energy (G) were also studied. The G data have been calculated from the equation [24]: G = -R T Ln k Where; R = gas constant = 8.3 J.mol-1.K T = absolute temperature (Kelvin) All results were recorded in Table (2). The negative value of (G) indicates that the reaction between (L1 and L2) and metal ions understudy are spontaneous. 174 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Molar Conductance All prepared complexes showed low molar conductance value in the solution (10-4M) ethanol and DMF at room temperature. The results indicate that they have non-ionic character Table (1) and well within the expected. which proposes a formula [ML2Cl2] where M(II) = (Zn, Cd and Hg). So the two chloride ions coordinated with metal ion [25]. Magnetic Susceptibility The magnetic susceptibility for all prepared complexes have been found to be diamagnetic (d10) (t2g6 eg4), and the electronic spectra don’t show any (d-d) band [26]. Spectroscopic Characterization FTIR Spectra and Mode of Binding The FTIR-spectra of the ligands (L1 and L2) and their prepared complexes were recorded in (CsI) over the range (200-4000 cm-1). The main vibrational bands have been assigned on the basis of the listed assignments of the FTIR spectra bands in the literature m [27, 28]. which are given in Table (3), while Figure (6-9) showed the spectra of (L1 and L2), [Zn(II)-L1] and [Cd(II)-L2]. As mentioned, the (L1 and L2) have different chelating sites. Thus a detailed translated of the spectra of (L1 and L2) and the effect of binding mode of metal ions under study on the vibration frequencies of the free ligands are discussed. The spectra of (L1 and L2) are showed a medium and broad band at (3423 and 3467) cm-1 respectively due to stretching vibration modes of (N-H) of the imidazole moiety [29]. The position of this band remained at nearly in the same region in the spectra of all prepared complexes, which may be explained its non involvement in the coordination of the two ligands to the metal ions [30]. The spectrum of (L1) has showed a sharp band at (1631) cm-1, while (L2) spectrum showed triplet band at (1647, 1623 and 1593 cm-1), can be attributed to stretching vibration of (C=N) of (N-3) imidazole nitrogen which is in agreement with the observation of previous authors [31], on coordination with metal ions, this band was observed with a little change in the shape and locale, these differences support of the π-acidic character of (-N=N-C=N-) azoimine moiety, while metal ions showed π-back donation and suggested the binding of metal ion with nitrogen atom for imidazole moiety [32]. The characteristic band in the spectra of free ligands (L1 and L2) at (1508 and 1492) cm-1 respectively attributed to stretching vibration (N=N), within shifts to lower wave number ( = 74-91) cm-1 in the spectra of the (L1-complexes) and ( = 17-88) cm-1 in the spectra of (L2-complexes), due to complex formation and presence (d MIIπ*) (azo of ligands) back donding [25]. At the far FTIR spectra for all prepared complexes showed new weak bands that are not present in the spectra of the ligands. These bands are located at (418-429) cm-1 which attributed to the (M- N) of an azo group and imidazole moiety [33]. As sell as another weak new band was appeared in the region (210-227) cm-1 which assignable to the (M-Cl) [28]. Thus the IR results lead to the proposal that the (L1 and L2) act as nutral N,N-bidentate chelate agent, coordinating through the nitrogen atom of azo group nearest to a naphthyl ring and N-3 atom of imidazole moiety to give five membered chelat ring. Based on the above, the proposed structure of the prepared complexes can be illustrated an octahedral as in Scheme (2). Electronic Spectra The UV-Vis. Spectra of (L1 and L2) and their prepared complexes were established in ethanol (10-4M) at room temperature in the region (200-1100) nm. All results are listed in Table (4), Figure (10-13). The value of molar extinction coefficient () of the two new ligands and their complexes in the range (1040-15490L.mol-1.cm-1), which leads to denote high sensitivity. The spectra of free (L1 and L2) have been appeared three bands, the first and the second bands were noticed at the ranges (205 and 242) nm and (248 and 289) nm 175 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 respectively. These two bands were attributed to (ππ*) transition of intra ligand charge transfer for imidazole and naphthalene moieties [34]. while the third band (max) was noticed at (387 and 375) nm, which owing to (ππ*) transition of intermolecular charge transfer from imidazole to naphthalene ring through the azo moiety [LMCT] [dπ(MII)π*(L)] transition[35,36]. On the other hand the (UV-Vis.) spectra for [Zn(II), Cd(II) and Hg(II)] complexes in ethanol solution have been showed high intense charge transfer [MLCT] transition as in Table (4). The 1HNMR Spectrum The HNMR spectra of the (L1 and L2) and the diamagnetic [Hg(II)-L1] complex were registered in DMSO solution with TMS as an internal standard. In the HNMR spectra for free azo ligands (L1 and L2) have noticed the main signals as in Figure (14 and 15), a signal of one proton at ( = 10.88 ppm) that approved the presence of carboxyl moiety in L-Histidine. As well as a singlet signal at ( = 8.42 ppm) attributed to (NH) proton of the imidazole moiety and don’t shift significantly in spectra of [Hg(II)-L1] complex compared with the ligand which indicate that the (NH) of imidazole moiety don’t involve in the coordination. At the same time the multiplet signals at ( = 6.96-7.10 ppm, 7H) and ( = 6.94-7.19 ppm, 6H) for (L1 and L2) respectively, referrer to aromatic protons of naphthyl and imidazole moieties. Slightly chemical shift was observed in the spectrum of [Hg(II)-L1] due to complex formation. Furthermore the doublet and triplet signals at high field in the spectra of free ligand (L1 and L2) due to aliphatic protons for (CH2) ( = 3.48-3.40 ppm) and (CH) ( = 3.8- 3.46 ppm), were noticed changes on coordination with metal ion [35]. Biological Efficiency All the prepared complexes and (L1 and L2) have been examined with Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria for the presence of antibacterial constituents, by using disc diffusion method [9]. The data are recorded in Table (5). The results explained that all prepared complexes have more toxicity than free ligands. So we owed to the Tweedy’s chelation theory [36]. Accordingly the coordination compounds reduce the polarity of metal ions due to the partial positive charge within doner moiety and in spite of the electron delocalization (dππ*) [MLCT] which leads to increase the lipophillic properties of chelating complexes, so performing it’s force during the lipid layers for the cell membrane. Otherwise the presence of the (C=N) and (N=N) group with active centers of cell component gives in the interference with normal cell process. Conclusion The N,N-bidentat (L1 and L2) were found to be linked with [Zn(II), Cd(II) Hg(II)] through the azo nitrogen neasrest to naphthyl moiety and the imidazole nitrogen. And so, atentative structure of the prepared complexes could be clarified as in Scheme (2). The characteristic of the lignads and their complexes have been studied by different physio- chemical techniques FTIR, HNMR and UV-Vis. Spectroscopies and elemental analysis gave satisfactory results corresponding to mole ratio of (1:2) metal to ligand after definition optimum pH and concentration at the (max). The (L1 and L2) and their prepared complexes have showed antibacterial efficiency. 176 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 References 1- Girish, B.V. and Zala, R.V. , (2011), “Synthesis and Analytical Studies of Some Azo Dyes as Ligands and Their Metal Chelates”, Int. J. Chem. Sci., 9,1, 87-94. 2- Wilson & Gisvolds., (2004) , “Textbook of Organic Medical and Pharmaceutical Chemistry”, Lippincott Williams and Wilkins, Philadelphia, 255-257. 3- Rokade, Y. & Sayyed R., (2009) , “Naphthalene Derivatives: a New Range of Antibacterials with High Therapeutic Value”, Rasāyan J. Chem., 2,4, 69-77. 4- Valentina, C.,(2012), “Azo Dyes Complexes. Synthesis and Tinctorial Properties”; U.P.B. Sci. 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Soc., 79,3, 303- 311. 29- Bellamy, L.J., (1980) , “The Infrared Spectra of Complex Molecules”, Chapman and Hall, London. 30- Senapoti, S., (2002) , Ray, U.S.; Santra, P.K.& Sinha, C., “Osmium-Azo Pyrimidine Chemistry, Part VII: Synthesis, Structural Characterization and Electrochemistry”, Polyhedron., 21, 753-762. 31- Alexander, D.& Minkin, V., (2004) , “Metal Complexes from Aryl and Heteroaryl Azo Compounds”, ARKIVOC, III, 29-41. 32- Sharma, R., Singla, M.& Kalia, K., (1996) , “Synthesis and Characterization of Some Tris (2-arylazophenolate) Rodium(III)) Chelates”, Indian Journal of Chemistry. 35A, 611-613. 33- Anilha, K.R.; Venugopala, R.& Vittala, Roa, K.S., (2011) , “Synthesis and Antimicrobial Evalution of Metal (II) Complexes of a Novel Bisazo Dye 2,2\- [benzene-1,3-diyldi(E)diazene 2,1-diyl]bis (4-chloroaniline)” , J. Chem. Pharm. Res., 3,3, 511-519. 34- Modhavadiya, V.A., (2011) , “Synthesis, Characterization and Antimicrobial Activity of Metal Complexes Containing Azo Dye Ligand of Sulfa Drugs”, Asian J. Bio. Chem. Pharm. Res., 13,4, 699-702. 178 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 35- Silverstein, R.M., Webster, F.X.& Kiemle, D.J., (2005) , “Spectrometric Identification of Organic Compounds”, 7th ed., Wiley, New York. 36- Rajasekar, K.; Balasubramaniyan, S.& Durairaj, P., (2014) , “Microwave Assisted Synthesis, Spectral, Antibacterial and Antifungal Activities of Cu(II) Complex with 4-aminoantipyrine and Oxalation”, World Journal of Pharmaceutical Research., 3,7, 844-849. Table (1): Synthetic physical and analytical data of ligands and their complexes Compound [M.wt. (gm/mole)] Color Yield% Elemental analysis Found (Calcd.)  ohm-1.cm2.mol-1 C% H% N% S% M% Cl% Ethanol DMSO L1 [389] Reddish brown 88 49.37 (49.35) 3.80 (3.76) 17.95 (17.99) 8.20 (8.22) - - - - [Zn(L1)2Cl2] [914] Red 74 42.00 (42.01) 3.20 (3.28) 18.56 (18.59) 7.01 (7.00) 6.78 (6.82) 7.47 (7.76) 8.43 7.81 [Cd(L1)2Cl2] [961] Pink 81 39.96 (39.95) 3.16 (3.12) 17.59 (17.68) 6.61 (6.65) 11.65 (11.60) 7.35 (7.38) 7.58 5.11 [Hg(L1)2Cl2] [1049] Reddish purple 72 36.66 (36.60) 2.81 (2.85) 16.27 (16.20) 6.20 (6.10) 19.11 (19.06) 6.61 (6.76) 9.38 8.16 L2 [405] Orange 85 47.49 (47.40) 3.81 (3.70) 17.30 (17.28) 7.78 (7.90) - - - - [Zn(L2)2Cl2] [946] Reddish purple 69 40.55 (40.59) 3.20 (3.17) 14.77 (14.79) 5.01 (6.76) 7.02 (6.87) 7.48 (7.50) 7.32 7.35 [Cd(L2)2Cl2] [993] Purple 73 38.47 (38.65) 3.18 (3.01) 14.20 (14.09) 3.16 (3.22) 11.28 (11.31) 7.09 (7.15) 4.89 6.93 [Hg(L2)2Cl2] [1081] Violet 67 35.64 (35.52) 2.60 (2.77) 13.01 (12.95) 5.78 (5.92) 18.49 (18.50) 6.58 (6.62) 6.28 8.55 Table (2): Metal:Ligand ratio , Stability constant and Gibbs free energy data Ligand Metal ion Optimum pH Optimum molar conc.×10-5 max (nm) M:L log G J.mol-1 L1 Zn(II) 7.0 7.0 518 1:2 8.328 -43.450 Cd(II) 7.0 7.0 484 1:2 8.069 -42.099 Hg(II) 7.0 7.0 429 1:2 8743 -45.615 L2 Zn(II) 7.0 6.5 570 1:2 8.428 -43.972 Cd(II) 7.0 7.5 546 1:2 9.019 -47.055 Hg(II) 7.0 6.5 550 1:2 7.980 -41.635 179 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Table (3): The main IR absorption bands of the ligands and their metal complexes in cm-1 units Compound (N-H) (C-H) Ar. (C=N) (N=N) (O=S=O) (M-N) (M-Cl) L1 3423 br.m 3060 v.w. 1631m. 1508 w. 1357 w. - - [Zn(L1)2Cl2] 3483 3060 v.w. 1655.3m. 1434 w. 1366 w. 345 w. 227w. [Cd(L1)2Cl2] 3481.2 3070.4v.w. 1656.7m. 1417 w. 1384.7 w. 329 w. 235 w. [Hg(L1)2Cl2] 3482 3066.6v.w. 1653m. 1421 w. 1367 w. 341 w. 225 w. L2 3467 m.br. 3051 v.w. 1647 1623 t.m. 1593 1492 w. 1338 w. - - [Zn(L2)2Cl2] 3470 m.br. 3060 v.w. 1612 1556 t.m. 1527 1475 1444 d.m. 1350 w. 418.6 w. 217 w. [Cd(L2)2Cl2] 3477 m.br. 3055 v.w. 1622 1595 d.m. 1568 sh.m. 1438 1404 d.m. 1346 w. 420 w. 212 w. [Hg(L2)2Cl2] 3475 m.br 3060.8 v.w. 1612 1598 t.m. 1569 1471 1436 d.m. 1346.2 w. 418 w. 210.2 w. w = weak, m = medium, v = very, b = broad, t = triplet Table (4): Electronic spectral data of the ligands and their complexes Compound max (nm) Absorption band (cm-1) Transition ×104 L.mol.-1.cm-1 L1 387 248 205 25839 40322 48780 ππ* 1.549 0.650 0.380 [Zn(L1)2Cl2] 518 19305 C.T. 0.221 [Cd(L1)2Cl2] 484 20661 C.T. 0.311 [Hg(L1)2Cl2] 429 23310 C.T. 0.513 L2 375 289 242 2666 34602 41322 ππ* 1.422 0.244 0.577 [Zn(L2)2Cl2] 570 17543 C.T. 0.156 [Cd(L2)2Cl2] 515,546 19417,18315 C.T. 0.398,0.465 [Hg(L2)2Cl2] 550 18181 C.T. 0.104 180 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Table (5): Antibacterial efficiency for the ligands and their complexes Compound E. coli gram (-) Staphyloccus aureus gram (+) L1 ++ + [Zn(L1)2Cl2] +++ ++ [Cd(L1)2Cl2] ++ ++ [Hg(L1)2Cl2] +++ +++ L2 ++ + [Zn(L2)2Cl2] ++ +++ [Cd(L2)2Cl2] ++ ++ [Hg(L2)2Cl2] +++ +++ (+) = 6-8 nm, (++) = 8-10 nm, (+++) > 10 mm Fig. (1): Calibration curve for [L1-metal ion] Fig. (2): Effect of pH on the absorption intensity of L1-complexes solution 181 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Fig. (3): UV-Vis spectra of : a-free Ligand (L1) solution, b-(L1-ZnII) mixed solution Fig. (4): Mole ratio for [L1-complexes solutions] Fig. (5): Mole ratio for [L2-complexes solutions] 182 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Fig. (6): FT-IR spectrum of the ligand L1 Fig.(7): FT-IR spectrum of the complex [Zn(L1)2Cl2] 183 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Fig.(8): FT-IR spectrum of the ligand L2 Fig. (9): FT-IR spectrum of the complex [Cd(L2)2Cl2] 184 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Fig. (10): UV-Vis. Spectrum of L1 Fig. (11): UV-Vis. Spectrum of [Hg(L1)2Cl2] Fig. (12): UV-Vis. Spectrum of L2 Fig. (13): UV-Vis. Spectrum of 185 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 Fig. (14): 1HNMR spectrum of the ligand L1 Figure No.(15): 1HNMR spectrum of the ligand L2 Fig. (15): 1HNMR spectrum of the ligand L2 186 | Chemistry 2015) عام 3العدد ( 28مجلة إبن الھيثم للعلوم الصرفة و التطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 28 (3) 2015 تركيبية والفعالية البايولوجية لليكندات آزو جديدة ومعقداتھا مع تحضير، دراسة [Zn(II), Cd(II) and Hg(II)]األيونات الفلزية علياء خضر عباس جامعة بغداد /كلية العلوم /قسم الكيمياء 2015/حزيران 23، قبل في : 2015/أيار/24 في:استلم الخالصة ـ L)1 مع ليكاندي االزو الجديدة غير المتجانسة الحلقة ,Cd(II) and Hg(II)][Zn(II)تم تحضير معقدات ل )2and L حامض سلفونيك مع -5-نفثول-1-امينو-7والمشتقة من التفاعل االزدواجي لملح الدايزونيوم لحامض النفثونك و من خالل التحليل الدقيق الھستدين في المحلول الكحولي القلوي. الصيغة التركيبية لجميع المركبات المحضرة شخصت للعناصر وقياس الحساسية المغناطيسية والتوصيلية الموالرية والدراسات الطيفية لالشعة تحت الحمراء واالشعة الفوق . فضال عن دراسة النسبة المولية لمعرفة نسبة الفلز:الليكاند لتحضير المعقدات باستعمال HNMRالمرئية و -البنفسجية . باستعمال مدى )max(عند الطول الموجي االعظم pHة بعد تثبيت الظروف المثلى من تركيز وطريقة النسبة المولي ) L:M) (1:2بير. جميع النتائج اثبتت ان النسبة المولية ھي كنسبة (-) التي ھي تطيع قانون المبرت5-10×8-6التراكيز ( ) تسلك كليكاندات 2Lو 1Lسطوح. اذ ان الليكاندين (ذات شكل ھندسي ثماني ال 2Cl2[M(L)[فلز:ليكاند والتي لھا الصيغة ترتبط مع الفلز عن طريق نتروجين مجموعة االزو القريبة من حلقة النفثالين ونتروجين الحلقة (-N,N)مخلبية ثنائية السن دراسة غير المتجانسة في الھستدين. كذلك اجريت دراسة ثابت االستقرارية والطاقة الحرة لكبس للمعقدات فضال عن .Staphylococus aureusو Escherichia coliالفعالية البايولوجية باستعمال الھستدين،ليكاندات اآلزو، الدراسات التركيبية، الفعالية البايولوجية : مفتاحيةكلمات