مجلة كركوك للعلوم Kirkuk Journal of Science

مجلة كركوك للعلوم Kirkuk Journal of Science

تحضير و تشخيص وقياس الفعالية البيولوجية لمعقدات ثنائية السن لليكاند قواعد شيف الحلقات الكبيرة ودراسة نظرية الكثافة الوظيفية (DFT)

نوع المقالة : بحث

المؤلفون
مرجان اسلام
سلوان محمد
قسم الكيمياء ⸲ كلية العلوم ⸲ جامعة دهوك ⸲ دهوك ⸲ العراق
10.32894/kujss.2026.168996.1283
الملخص
تم تحضيرو تشخيص سلسلة جديدة من معقدات قواعد شيف الحلقات الكبيرة الثنائية النواة ذات الصيغة العام [M₂LCl₄] M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) L = (2Z,10Z,13Z,21Z)-3,10,14,21-tetraaza-1,12(1,4)-dibenzenacyclodocosaphane-2,10,13,21-tetraene عن طريق تفاعل تكثيفي بنسبة 2:2 بين الترفثالديهايد والهكساميثيلين ثنائي الأمين وتم الحصول علي ليكاند حلقة كبيرةمن نوع (N4 ) . وتم تشخيص المعقدات المحضرة عن طريق الحساسية المغناطيسية واطياف الرنين النووي المغناطيس للبروتون 1 والكاربون 13 وطيف تحت الحمراء والاشعة فوق البنفسجية والتوصيل الكهربائي والفعالية البايولوجية ودراسة نظرية للصيغة الجزيئية والتركيب الفراغي. وتشير البيانات الطيفية والتحليلية والمغناطيسية مجتمعةً إلى وجود هندسة رباعية السطوح حول المراكز الفلزية في جميع المعقدات باستثناء معقد النحاس الثنائي Cu(II)، الذي يُظهر هندسة مستوية مربعة. كما أظهرت المعقدات سلوكًا لا غير موصل في المحلول، كما استُدل عليه من قياسات التوصيلية المولارية. استُخدمت طريقة الانتشار بالأقراص لتقييم الفعالية المضادة للبكتيريا لكلٍّ من ليكاند قاعدة شيف ومعقداته الفلزية. وقد أظهرت النتائج أن التناسق مع الفلز يعزز بصورة ملحوظة قدرة الليكاند على تثبيط نمو البكتيريا موجبة الغرام وسالبة الغرام، Staphylococcus aureus, Escherichia coli، Klebsiella pneumoniae كما أُجريت حسابات نظرية الكثافة الوظيفية (DFT) عند مستوى B3LYP باستخدام مجموعة الأساس LANL2DZ للذرات الفلزية و 6-311++G(d,p) للذرات اللافلزية. وقد وفرت هذه الحسابات الهندسيات المثلى، وطاقات HOMO–LUMO، والمعلمات الثرموديناميكية، مما دعم النتائج التجريبية وقدم فهماً أعمق لتآثرات الفلز–الليكاند التي تتحكم في ثباتية المعقدات وتفاعليتها.
الكلمات الرئيسة
ليكاند قاعدة شيف كبير الحلقة
مانح N4
النشاط المضاد للبكتيريا
نظرية دالة الكثافة (DFT)
ثنائي النواة
Crossmark
الموضوعات

1. Introduction 

   Schiff bases constitute a broad class of organic compounds characterized by the presence of an imine (-C=N-) functional group [1], [2], [3]. They are typically formed through the condensation reaction between aliphatic or aromatic amines with aldehydes or ketones containing a reactive carbonyl group [4]. The formation of Schiff bases generally proceeds via nucleophilic attack of the amine on the carbonyl carbon, followed by elimination of water. Depending on the electronic properties of the substrate, this process can be accelerated by either an acid or base catalyst, or by the application of elevated temperature [5], [6]. The broad applicability of Schiff bases is primarily attributed to the strong donor ability of the azomethine nitrogen atom, which acts as an effective electron donor and enables Schiff bases to coordinate readily with metal ions, thereby attracting considerable scientific interest in both ligand design and metal-complex synthesis [7]. Schiff bases are substantial due to their stability, chelating properties, and biological applications [8]. The rise of antibiotic-resistant organisms has increased the importance of identifying new antibacterial medicines with improved selectivity and reduced toxicity [9]. Schiff bases and their metal complex have also been shown to have antibacterial, antifungal, and anticancer properties [10]. They are effective antibacterial agents, and metal complexation has been shown to enhance their biological activity and alter microbial response [11], [12].

    Schiff-base macrocyclic ligands and their metal complexes represent an essential class of compounds that have been extensively investigated. Macrocyclic tetradentate Schiff base ligands are significant in coordination chemistry due to their four donor sites, which provide robust and versatile binding [13], as shown in Figure 1. The synthesis of tetraazamacrocyclic complexes has been significantly aided by condensation reactions between diketones and primary diamines in the presence of metal ions.The metal facilitates the process by directing the steric course toward cyclic molecules rather than polymeric structures. Macrocyclic complexes exhibit greater thermodynamic stability and enhanced selectivity as ion binders compared to their open-chain analogs [14], [15]. Their cyclic framework generates stable metal complexes with various structural features, making them significant in catalysis, bioinorganic chemistry, and medical applications [16].

Macrocyclic Schiff ligands, particularly when coordinated with transition metals, have attracted significant attention because of their structural diversity and their ability to influence the physicochemical and biological properties of the resulting metal complexes [17]. In the present study, a novel Schiff Base Ligand and symmetrical binuclear azomethine complexes of Mn(Ⅱ), Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cu (Ⅱ), and Zn(Ⅱ), These complexes were prepared through the condensation of Terephthalaldehyde and 1,6-hexamethylenediamine (Figure 2). The tetradentate Schiff base ligand and all complexes (1-6) were identified and characterized using NMR, IR, UV-Visible spectroscopy, atomic absorption, molar conductivity, and magnetic moment measurement. They were examined for their antibacterial efficacy against Escherichia coli, Staphylococcus aureus, and Klebsiella Pneumonia to assess the influence of metal-ion identity and macrocyclic coordination on biological effectiveness.

      Furthermore, Density Functional Theory (DFT) calculations were carried out using the B3LYP functional. The 6-311++G(d, p) basis set was used for non-metal atoms (C, H, and N), while the LANL2DZ basis set was employed for the transition metal ions. Gaussian 16 software was used for geometry optimization and the calculation of structural parameters, including bond lengths and bond angles. The frontier molecular orbitals (FMOs),(HOMOs and LUMOs)were also investigated. The global reactivity descriptors were derived from FMO energy-level analysis. Providing optimized geometries, HOMO–LUMO energy gaps, and electrostatic potential assessments of the molecules. The thermodynamic parameters were calculated in both the gas and solvent phases to evaluate the effect of solvation on the stability of the studied compounds. 

Figure 1: The macrocyclic formation reaction, where A and B represent aliphatic or aromatic(dialdehyde and diamine),n is the number of moles of M(Ⅱ) transition metals.

2. Materials and Methods

 All solvents and reagents used in this work were of analytical quality. Most chemicals were supplied by the University of Duhok, including MnCl₂·4H₂O, FeCl₂·4H₂O, CoCl₂·6H₂O, NiCl₂·6H₂O, CuCl₂·2H₂O, ZnCl₂, hexamethylenediamine, ethanol, and diethyl ether. Additionally, Terephthalaldehyde was purchased from Bide Pharmatech Ltd, glacial acetic acid from Scharlau, and DMF from Thomas Baker. The ¹H and ¹³C-NMR spectra of the synthesized ligand were recorded on a Bruker Ultra Shield 500 MHz NMR spectrometer in CDCl₃ at 298 K. FTIR spectra were obtained using a Shimadzu FTIR-8400S spectrophotometer in the 4000–400 cm⁻¹ range with KBr discs. Magnetic susceptibility measurements were performed in the solid state at 298 K using a Sherwood Scientific magnetic balance. Electronic absorption spectra were recorded at 25 °C in DMF using a Jenway 6800 double beam UV–Vis spectrophotometer 10⁻³ M with 1 cm quartz cells. The melting and decomposition temperatures of the ligand and its complexes were determined using an electrothermal melting point apparatus. Molar conductivity measurements were carried out using a 4520PH conductivity meter for 10⁻³ M DMF solutions at 25°C. Metal ion contents of the complexes were finally quantified using an AA-670G Atomic absorption spectrophotometer. The disc diffusion method was used to measure antibacterial activity. The geometries and energies of these compounds were assessed using Gaussian 16W.

2.1.Synthesis of Schiff Base Ligand [C28H36N4].

 The synthetic route of the macrocyclic Schiff base ligand by mixing (0.02mol, 2.6822g) Benzene-1,4-dicarboxaldehyde in 70ml of ethanol with (0.02 mol, 2.323g) hexamethylenediamine in 50ml of ethanol, under continuous magnetic stirring. Subsequently, three droplets of glacial acetic acid were added as a catalyst. The reaction mixture was refluxed for 8 hours at 80 °C. The precipitate formed was then filtered, thoroughly washed with ethanol and diethyl ether, and dried in vacuo over anhydrous CaCl2. A pale-yellow solid was obtained, yielding 4.0751 g (95.09%) and a melting point of 176 °C. H-NMR, 500 MHz; CDCl₃) δ 8.27 (s,1H), 7.747 (s, 2H), 3.62 (t, 2H), 1.77 – 1.35 (m, 4H).13C-NMR (125 MHz, CDCl3) δ 160.28, 138.07, 128.23, 77.03, 76.77, 61.83, 30.81, 27.17.

 

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مجلة كركوك للعلوم Kirkuk Journal of Science
السنة 21، العدد 2
الربيع 2026
الصفحة 1-23

  • تاريخ الاستلام 26 كانون الثاني / يناير 2026
  • تاريخ التعديل 24 نيسان / أبريل 2026
  • تاريخ القبول 24 نيسان / أبريل 2026