198 This work is licensed under a Creative Commons Attribution 4.0 International License IHJPAS. 37 (1) 2024 Ibn Al-Haitham Journal for Pure and Applied Sciences Journal homepage: jih.uobaghdad.edu.iq PISSN: 1609-4042, EISSN: 2521-3407 1Asmaa Edrees Fadhil* 2Alyaa Khider Abbas 1,2 Department of Chemistry, College of Sciences, University of Baghdad, Baghdad, Iraq. *Corresponding Author: asmaa.idrees1205m@sc.uobaghdad.edu.iq Abstract Azo dyes are the most common and widely used dyes, accounting for more than half of each year's dyes. In this work, a complete description of a new innovative series of compounds with the elements [Ag (I), Zn (II)] generated from the guanine azo dye ligand (GAB) 8-[1-(3- carboxy) azo] guanine has been studied. The structural formula was studied using several physicochemical analyses and spectroscopic techniques (FT-IR spectra, UV-Vis). The FTIR spectrum of the ligand (GAB) was compared to the spectra of the metal ion complexes formed to determine its identity. Chelating caused some changes in the spectra of the complexes to appear to demonstrate that they could be linked to the ligand. The complexes have a tetrahedral geometry shape, the ligand functions as a bidentate ligand, and thermogravimetric analysis (TGA) is used to measure the thermal stability of compounds. The findings and equation presented by the analytical data seemed to be in good accord with the conclusions of the thermogravimetric investigation, which demonstrated that the disintegration of the ligand (GAB) and its complexes occur in multiple steps. The configuration that follows weakens thermal stability: GAB(35.52%)>[Ag(GAB)(H2O)2]NO3.2H2O(34.6%)>[Zn(GAB)Cl2].H2O(31.54%), and the complexes have tetrahedral geometry shape. Furthermore, elemental analysis, mole ratio, and the mole ratio of each complex (1:1) (M:L). The ligand was effective as an acid-base indicator when the pH changed; they exhibited a striking color change, similar to how the ligand (GAB) and its complexes can be used to dye wool textiles due to their wide range of colors. It investigated how well the ligand (GAB) and its complex worked as a wool dye. The ligand GAB and its metal complexes were used to color most of the protein filaments in wool fiber, which have a complex structure with amino and carboxyl groups and colors ranging from orange to green. Keywords: Azo dyes, Acid-base indicators, Dying performance, Guanine, Thermogravimetric analysis. Received 26 January 2023, Received 24 March 2023, Accepted 30 March 2023, Published 20 January 2024 Guanine Metal Complexes: Spectroscopic Studies, Dying Performance and as Indicator doi.org/10.30526/37.1.3242 https://creativecommons.org/licenses/by/4.0/ https://jih.uobaghdad.edu.iq/index.php/j/index#1609-4042 https://jih.uobaghdad.edu.iq/index.php/j/index#2521-3407 mailto:asmaa.idrees1205m@sc.uobaghdad.edu.iq https://orcid.org/0000-0003-4195-8824 mailto:asmaa.idrees1205m@sc.uobaghdad.edu.iq https://orcid.org/0000-0002-8400-0926 mailto:alyaa.abbas@sc.uobaghdad.edu.iq IHJPAS. 37 (1) 2024 199 1. Introduction Azo dyes account for most of the dye chemistry production volume, and their importance may grow. They are critical for the management of the dye and printing markets. These dyes are made using a simple diazotization and coupling technique. Many paths and changes are taken to achieve the dye's desired color characteristics, yield, and particle size for better dispersibility [1, 20]. Indicators include dyes or pigments that can be extracted from plants, fungi, and algae. Anthocyanins, also known as flavonoids, are a form of organic pigment that varies in color depending on the pH. It could be found in almost every red, blue, or violet flower. Anthocyanidins (anthocyanins) are essential plant pigments that cause the red, violet, and blue colors found in plant blossoms [2]. Previous research has revealed that commercially used markers come from natural sources or chemical synthesis. Acid-base indicators are structurally divided into three groups: phthaleins (e.g., phenolphthalein), sulphonaphthaleins (e.g., phenol red), and azo compounds (e.g., methyl orange) [2]. As their chemical forms change due to changes in their chemical environment, these compounds change color. Azo dyes are the most common synthetic colorants, and they are widely employed in the textile, printing, and paper industries [3,27,28]. Different colors can be produced by altering the functional groups integrated into the azo molecule. The main aim of this work is to prepare the [Ag (I), Zn (II)] complexes derived from the ligand (GAB) and identify them with some physicochemical methods. 2. Materials and Methods Solvents, materials, and tools were employed in each instance (C.H.N.) to determine the elemental analysis of the ligand (G.A.B.) and its complexes using an Eure EA 3000 Elemental Analyzer. When testing the pH of a sample, (HANNA equipment) was used. FT-IR spectra were acquired by using C.S.I. and a SHIMADZU 8400 spectrophotometer. The UV-Vis spectra of all the chemicals under investigation were examined using the (SHIMADZU 1800 UV-Vis spectrophotometer). Thermal gravimetric analysis (TGA) (S.D.T., Q600 V20.9 Build) was used to determine how much metal was in the synthesized ligands and complexes. Each chemical's melting points were determined using Gallenkamp's melting point equipment. The molar conductance of metal ion complexes was measured in deionized pure water at (10-3 M). The Mohr method was utilized to determine the chloride content in complexes. 2.1 Synthesis of the ligand 8-[1-(3-carboxy) azo] guanine (GAB) A modified version of the procedure published in the literature [4, 21] was used to manufacture the ligand [GAB] (the diazonium reaction and coupling). The ligand [GAB] was synthesized by dissolving (0.01 mole; 1.371 g) m-aminobenzoic acid in (30 mL) ethyl alcohol, followed by a 4ml addition of concentrated acetic acid at (0-5°C). A cooled aqueous sodium nitrite solution (0.83 g in 25 mL water) was added to this solution with continuous stirring and held at approximately (0- 5°C). The diazonium salt solution was slowly stirred into a cold solution (0.01 mole; 1.94 g) of guanine dissolved in [14 mL, 10% ethanolic NaOH solution]. The resulting liquid was neutralized to a pH of 5-6 by adding acetic acid or sodium hydroxide. The orange precipitate was filtered and IHJPAS. 37(1)2024 200 washed with a [distilled water: ethanol] [1:1] mixture before being gathered and desiccated [22] (Scheme 1). Scheme 1. Synthesis of the ligand (GAB ( 2.2 Synthesis of metal complexes The synthesis of complexes was done in a mole ratio of [M:L] [1:1] by dissolving (1 mmol; 0.299 g) of the ligand GAB in a minimum quantity of deionized distilled water. The ligand solution was added gradually, with stirring, to the selected aqueous solution of metal salts [1 mmoL from each of AgNO3 0.1698 g or ZnCl2 0.1362 g], which were dissolved in the deionized distilled water. The mixture was refluxed for 3 hours, and the reaction was monitored using the TLC technique with the mixed solvent [0.8 mL methanol, 1.2 mL ammonia, and 0.4 mL butanol]. After filtering the colored solid, the residue is washed with a mixture of deionized distilled water and ethanol (1:1), then filtered and dried. The physicochemical properties of the ligand (GAB) and its complexes are tabulated in Table 1 [5]. Table 1. Physical features and elemental properties No. Comp. (M.wt) (g/mol) Color λmax (nm) M:L Ʌm (S.mol-1. cm2) % Experimental % (Theoretical) C H N M Cl 1 GAB(C12 H 9N 7O3) 299.27 Yellow 435.00 --- --- 48.142 48.117 3.007 3.955 32.086 32.743 --- --- 2 [Ag(GAB)(H2O)2]NO3.2H2O 516 Yellowish orange 476.00 1:1 82.1 29.871 30.232 2.918 2.519 21.299 21.705 20.905 20.502 --- 3 [Zn(GAB) Cl2].H2O 453.65 Reddish orange 492.00 1:1 25.7 31.729 31.472 2.285 2.424 21.602 21.607 14.412 14.951 3.751 3.022 IHJPAS. 37(1)2024 201 3. Results and Discussion 3.1 Mole ratio The most widely used technique for determining a complex's composition in solution is the mole ratio approach, which was applied in this case. Figure 1 displays this process, the locating outcomes it produced, and Table 2 presents the data. The results show that all the complexes built have a [1:1] ratio [M: L] mole ratio [6]. Figure 1. The mole ratio plot of complexes' Table 2. Absorbance vs mole ratios for GAB-metal ion in solution 3.2 Thermogravimetric analysis (TGA) The thermal behavior of the ligand (GAB) and its complexes during the ligand GAB degradation happens in four exothermic steps in the 50–800 °C range. The first stage of disintegration is between 25 and 50°C, resulting in a 2.11% weight loss; the second stage occurs between 50 and 290 °C, resulting in a 26.79% weight loss; and the third stage occurs between 290 and 600°C, resulting in a 25.61 weight loss. Between 600 and 800°C, the final stage of disintegration begins (9.356% weight loss). The suggestion is in Figure 2A. In the instance of [Ag(GAB)(H2O)2] NO3.2H2O, there are five steps, and the complex degrades Figure 2B. The first stage of M:L Absorbance (λmax nm) GAB-Ag 476 GAB-Zn 492 1:0.25 0.172 0.01 1:0.50 0.194 0.103 1:0.75 0.279 0.141 1:1 0.278 0.165 1:1.25 0.277 0.178 1:1.50 0.285 0.172 1:1.75 0.284 0.177 1:2 0.287 0.178 1:2.25 0.285 0.187 1:2.50 0.288 0.183 1:2.75 0.286 0.185 1:3 0.285 0.187 1:3.25 0.289 0.182 1:3.50 0.287 0.18 1:3.75 0.291 0.184 1:4 0.289 0.183 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0.22 0.24 0.26 0.28 0.3 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 A B S. MOLE RATIO CM/C CAG-Ag CAG-Zn IHJPAS. 37(1)2024 202 decomposition begins at 25 to 80°C, resulting in a weight loss of 2.86 kg of decomposed water [18]. The second breakdown stage was seen at 80–400°C (11.78% weight loss). Decomposition begins in the third stage at 400–500°C (12.80% weight loss). The fourth stage begins with a temperature range of 500–675°C (27.39% weight reduction). The last was at 675-800°C (a weight loss of 10.04%) [7]. Concerning [Zn(GAB)Cl2]. The H2O complex is divided into five steps Figure 2 d. The initial stage of decomposition begins at 25 to 55°C, resulting in a loss of 1.434 pounds. Between 55 and 84°C, the second stage of breakdown (17.63% wt loss) was observed. The third stage of decomposition begins between 84 and 560 (18.84% weight loss). Starting at 560–698°C, the fourth stage is 16.73% of its weight. The last stage is 698–800°C (13.83% weight loss) [8,9]. The findings and equation presented by the analytical data seemed to be in good accord with the findings of the thermogravimetric investigation, which demonstrated that the disintegration of the ligand (GAB) and its complexes occurs in multiple steps. The configuration that follows weakens thermal stability: GAB(35.52%)>[Ag(GAB)(H2O)2]NO3.2H2O(34.6%)>[Zn(GAB)Cl2].H2O(31.54%) Table 3. The TGA of ligand (GAB) and their complexes Comp. & Molecular formula(molecular weight) g/mole Step TG. Range of the decomposition (0C ) Suggested Assignment % Mass loss Cal. % Found % GAB C12H9N7O3 1 (25-50) H3C0.25 2.00 2.117 2 (50-290) H2C6.5 26.73 26.79 3 (290-600) H4C5.25N0.6 25.19 25.619 4 (600-800) N2 9.356 9.967 Residue >800 N4.4O3 36.62 35.52 [Ag(GAB)(H2O)2]NO3.2H2O AgC13H13N8O8 1 25-80 H2O 3.488 2.867 2 80-400 H2O.C3H6 11.62 11.78 3 400-500 C5H3 12.2 12.80 4 500-675 C5N5 27.90 27.39 5 675-800 N2O1.5 10.07 10.04 Residue >800 AgO4.5 34.6 35.09 [Zn(GAB) Cl2].H2O ZnC12H11N7O4Cl2 1 25-55 H2O0.25 1.32 1.434 2 55-84 Cl2C 18.29 17.63 3 84-560 C7H3 19.17 18.84 4 560-698 C4O1.50H6 17.19 16.73 5 698-800 N2O2 13.22 13.83 Residue >800 ZnN5O0.75 32.40 31.54 IHJPAS. 37(1)2024 203 Figure 2. Thermogram for the (a) GAB ligand (b) [Ag(GAB)(H2O)2]NO3.2H2O (c) [Zn(GAB)Cl2].H2O complexes 3.3 The FTIR spectra for GAB ligand and its complexes The FTIR spectra analysis can be utilized to determine how the ligand (GAB) will connect the metal ions to the formed complexes. The FTIR spectrum of the ligand (GAB) was compared to the spectra of the metal ion complexes formed to determine its identity. Chelating caused some changes in the spectra of the complexes to appear to demonstrate they could be linked to the ligand [29,30]. Table 4 summarizes the principal bands for the ligand (GAB) and its metal ion complexes, whereas Figure 3 shows the most moieties vibration was carried out in the range 400–4000 cm-1 using CSI disk [10, 11, 17]. a b c IHJPAS. 37(1)2024 204 Table 4. The FT-IR spectrum for the free ligand (GAB) and its complexes Figure 3. The FTIR assignment for the (A) GAB ligand (B) [Ag (GAB) (H2O)2]NO3.2H2O (C)[Zn(GAB)Cl2].H2O complexes Com. ʋ (OH) ʋ (NH2) ʋ (C=O)py ʋ (C=N)imd ʋ N=N ʋ (-CN=N-C-) ʋ (M-N)imd ʋ (M-N) azo ʋ (M-Cl) ʋ (MO) H2O GAB 3344 b [3174 3112 d [1691 1668 ] d 1573 Sh. [1473 1419 1373] t 1259 W --- --- --- --- [Ag(GAB)(H2O)2] NO3.2H2O 3342 m [3166 3114] d [1693 1672] d 1560 w [1415 1375]d 1261 W 603 w 503 w --- 459 vw [Zn(GAB) Cl2].H2O 3342 m [3172 3114] d [1693 1672] d sh. 1564 w [1415 1375] d 1263 w 605 w 503 vw 418 vw --- C B A IHJPAS. 37(1)2024 205 3.4 Electronic spectrum of the (GAB) ligand and its complexes The electronic spectra of the ligand (GAB) and its complexes were dissolved in water [10-4 M] with the range (280-1100) nm. The data of the ligand and its complexes are shown in Table 5 and Figure 5 [12,13,19]. Table 5. The data of spectrum of UV-Vis for (GAB) ligand and their complexes Figure 4. The electronic spectra for (A) GAB ligand (B) [Ag(GAB)(H2O)2]NO3.2H2O (C) [Zn(GAB)Cl2].H2O 3.5 Dying performance The effectiveness of the ligand (GAB) and its complex as a wool dye were examined. Most of the protein filaments in wool fiber, keratin, have a complex structure with amino and carboxyl groups [14]. Keratin is also the majority of the protein filaments in wool fiber. Early theories of wool dyeing were developed on the wool's ability to absorb acids. Interactions between the negatively charged dye anions and the positively charged amino groups on the fibers could explain the entire process of dying wool in an acidic environment. Polar groups like -NH, -SH, and -OH are among Compound ℷ(𝑛m) Wavenumber )1-cm( Assignment Hybridization Geometry GAB 291 409 34364 24449 𝜋 → π ∗ n →π* --- --- [Ag(GAB)(H2O)2]NO3.2H2O 476 21008 CT Sp3 Tetrahedral [Zn(GAB) Cl2].H2O 492 2032 CT Sp3 Tetrahedral A B IHJPAS. 37(1)2024 206 the numerous polar groups discovered in wool fiber. In polyamide fiber, a terminal amino group and a sizable number of NH groups are conceivable. A specific pH level is required for these functional groups to interact covalently with reactive dyes such as vinyl sulphone and chlorotriazine. It is important to emphasize that this is happening in an acidic environment. Numerous variables, such as the type of metal and its valence state, the concentration of the solution, pH, time, temperature, and others, affect the amount and rate of absorption. The free carboxyl groups of acidic amino acids are the most likely binding sites because they can offer negatively charged binding sites over a wide pH range. Particularly at alkaline pH values, the nitrogen atoms of amin and amide groups can form coordination linkages [15]. The wool fabric in Figure 5, which has colors ranging from orange to green, was colored using the ligand GAB and its metal complexes [25,26]. Table 6. Data on coloring and different fastness characteristics of GAB ligands and complexes on wool textile 3.6 Azo dyes as acid-base indicators Organic dyes with distinct colors in solutions with different pHs are known as acid-base indicators. They are frequently used in acid-base titrations to establish the equivalency point. When the pH changes, they exhibit a striking color change. Due to their capacity to alter color in response to pH, azo dyes are the most widely used chemical molecules as acid-base indicators [16,23,24]. Table 7 contains the data from acid-base titrations, which is used to assess the indicator properties of azo dyes. Figure 6 displays the azo dye solutions in both acidic and basic environments. Compounds Color Color fastness Staining Dye Notes GAB Yellow 4 4 Acceptable on grayscale [Ag(GAB)(H2O)2]NO3.2H2O Yellowish orange 3 3 Acceptable on grayscale [Zn(GAB) Cl2].H2O Reddish orange 4 4 Acceptable on grayscale A B C Figure 5: The dying of ligand (GAB) and some of their complexes A=GAB ligand ,B=[Ag(GAB)(H2O)2]NO3.2H2O,C=[Zn(GAB) Cl2].H2O . IHJPAS. 37(1)2024 207 Table 7. Titration of acid (0.1M) against NaOH (0.1M) for (GAB) Figure 7. Change in color of Azo ligand (GAB): A= HCl with NaOH, B= ACOH with NaOH, C=HCl with NaHCO3, D= ACOH with NaHCO3 4. Conclusion The Ag (I) and Zn (II) complexes were from the azo ligand 8-[1-(3-carboxy)azo]. The mole ratio at which guanine (GAB) is produced is [M:L][1:1]—and studied using various spectroscopic methods. The complexes have tetrahedral geometry; the ligand functions as a bidentate ligand. They can be used as a suitable indicator for acid-base titrimetric assays in solid acid/strong base and weak acid/strong base titrimetric analyses. The ligand and its complexes have a variety of colors that have been confirmed to be used for dying wool fabrics, and the result of the ultraviolet protection factor shows a good UV-absorbing ability. The primary goal is to assist with various analytical tasks in research and teaching labs. Acknowledgment The authors thank the Department of Chemistry/ College of Science/ University of Baghdad staff for their assistance in performing this research. NO. Volume of acid Volume of NaOH volume of NaHCO3 (mL) Color in acid Color in base 1 (HCl) 5 mL 5.3 mL --- Dark yellow Light yellow 2 (ACOH) 5 mL 6 mL --- Yellow Color less Titration of acid (0.1M) against NaHCO3 (0.1M)for (GAB) 3 (HCl) 5 mL --- 7.3 mL Yellow Color less 4 (ACOH) 5 mL --- 6 mL Light yellow Yellow Hard acid Hard base Weak acid Hard base Hard acid Weak base Weak acid Weak base IHJPAS. 37(1)2024 208 Conflict of Interest The authors declare that they do not have any competing interests. Funding There is no financial support. Ethical Clearance This work has been approved by the Scientific Committee at the University of Baghdad/ College of Science. References 1. Benkhaya, S.; M'rabet, S.; El Harfi, A. Classifications, properties, recent synthesis and applications of azo dyes. Heliyon, 2020, 6(1), e03271. https://doi.org/10.1016/j.heliyon.2020.e03271. 2. Alexander, B.; Imran, A.; Tewelde, S.; Ahmedin, H.; Ghebray, A.; Roop, C. 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