CC BY
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ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
AZERBAIJAN CHEMICAL JOURNAL № 2 2023
163
UDC 546.817; 847.583; 548.737
SUPRAMOLECULAR NANOSTRUCTURED COORDINATION POLYMER BASED ON A NICKEL COORDINATION COMPOUND WITH PYROMELLITIC ACID
M.K.Munshiyeva\ F.B.Aliyeva1. S.R.Mamedova1. P.S.Safarova2 , 2M.M.Qasanova
B.T.Usubaliyev
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, Ministry of Science and Education of
the Republic of Azerbaijan 2 Azerbaijan State Oil and Industry University, Scientific Research Institute Geotechnological
Problems of oil, gas and chemistry
fira.chemstry@mail.ru
Received 03.11.2022 Accepted 27.01.2023
{[Ni2C6H2(COO)4(H2O)4]-H2O2,5}n binuclear coordination compound with supramolecular structure has been synthesized. The composition and chemical structure of the coordination compound have been determined by the elemental, X-ray, IR spectroscopic and differential thermal analyzes. The unit cell parameters have been determined by identifying the diffraction pattern and the inferred schematic structure of the two-dimensional polymer layer of the coordination polymer, which is the building block for all the studied coordination compounds from this series, has been given. The layers are connected with each other and shifted relative to each other depending on the direction and strength of the hydrogen bonds; and this leads to a change in the parameters of the unit cells. Thus, two-dimensional polymer layers (2D) are transformed into a 3D supramolecular structure.
Keywords: coordination compound, coordination polymer, hydrogen bond, 2D structure, 3D structure, IR spectrum, thermal decomposition, supramolecule.
doi.org/10.32737/0005-2531-2023-2-163-168 Introduction
Supramolecular nanostructures, which are of great importance for materials science, are based on organic molecules arranged in complex, hierarchical nanostructures [1-4].
Starting from the molecular level, the organization of such nanostructures includes the design of solid-state architecture by the way of appropriate selection of molecules. In this sense, coordination polymers which are formed by central metal ions binding with various ligands through coordination bonds are of great importance. For the past decade, they have attracted a lot of attention due to their amazing structures, and more importantly, their potential applications, among others, in catalysis, gas storage, luminescence and sensing [5-10]. Their final solid-state structure is controlled by a self-assembly process in which, one-, two-, or three-dimensional structures are formeddepending on the chosen building blocks. The building blocks of coordination polymers determine their physicochemical properties [11-17].
Ni (II) coordination polymer has been synthesized with benzenetetracarboxylic acid (pyromellitic acid) and studied by complex methods of physicochemical analysis.
Experimental part
The reagents have been acquired from commercial sources and used without additional purification (as such).
X-ray phase analysis has been performed on a Commander Sample ID instrument (Coupled Two Theta) with a copper cathode.
The IR absorption spectrum has been recorded on Thermo Scientific Nicole 1810 instrument in the range of 400-4000 cm-1. Samples have been prepared as suspensions in vaseline oil.
Derivatograms have been recorded on STA-449 F-3 derivatograph (Germany) in a nitrogen medium.
Elemental analysis for C, H has been fulfilled on ERBA CHNSO<<E>> analyzer. The metal content has been calculated from the
weight loss curve according to the amount of oxide obtained after heating to 800°C on the derivatograph.
NiCh^O, NaHCO3 (chemically pure) and pyromellitic acid (chemically pure) have been used for the synthesis of the complex compound.
The compound has been obtained as a result of the stoichiometric reaction of the metal and ligand (2:1) in aqueous solution. At first, 100 ml of distilled water has been gradually added to 1 mol of pyromellitic acid, and then 1 mol of NaHCO3 has been added in portions in an aqueous medium with stirring at 800C to obtain the complex. Aqueous solution of 2 mol NiCl26H2O salt has been added to the resulting hot solution and the latter was left to cool to room temperature and filtered. The resulting precipitate has been, first, washed several times with distilled warm water and then with benzene, and first, dried in air and then in an oven at 500C. The color of the polycrystalline powder is emerald. The yield of synthesis product is 85%.
Results and discussion
Analytical calculation for the synthesis product: C 24.79%; H 3.05%; Ni 24.38%; O and others 47.78. According to the result of the
elemental analysis, the chemical formula of the coordination compound is Ni2L(H2O)6.5 (L-C6H2(COO)4), (M=484.50).
The X-ray diffraction pattern of the synthesized compound is shown in Figure 1.
35 reflexes have been fixed in the recorded diffraction pattern of the obtained coordination polymer. Analysis and interpretation of the interplanar distances showed that the given compound is crystallized in orthorhombic syngony with the following unit cell parameters: a=9.59, b=8.29, c=15.08. The volume of the unit cell is Ve.c=1198.41Â.
In the IR spectrum of the coordination compound (Figure 2) showed that adsorption band appears in the region of 1574.46 and 1462.80cm-1, which refers to the asymmetric (vas) and symmetric (vs) oscillation of carboxyl groups of tetraanionpyromellitic acid (benzene tetracarboxylic acid). The value of the difference A[va (CO-) -vc (CO-) ], which is 111 cm-1, shows that the carboxylate anions of pyromellitic acid have a bidentate chelating functionality [18, 19].
In addition, there is a broad band in the IR spectrum in the region of 3600-3200 cm-1, which refers to molecules of crystallization water.
10 20 30 40 SO M T®
2Th«la (Ciiuoteo TwoTheta/Theta* WL=1 54080
Fig.1. X-ray pattern of the coordination polymer
isoq 30» 2sco aaoo 1300 1000 sod
Wave number (cm
Fig.2. IR spectrum of the coordination polymer.
Fig.3. Thermogram of the coordination polymer.
Thermogravimetric analysis has been carried out in the temperature range of 20-9000C (heating rate 100/min, Al2O3 standard, N2 atmosphere, TG corr./range.meas. 000/35000 mg).
From the derivatogram of the coordination compound presented in Figure 3, it can be seen that decomposition occurs with a sharply defined endothermic effect with a maximum at a temperature of 111.70C that corresponds to the removal of 2,5 water
molecules. In this case, the weight loss is experimentally 13.75% (calculated 14.34%) of the total mass.
The second endothermic effect is observed at a temperature of 161.90C, which also corresponds to the removal of 4 water molecules. In this case, the weightloss is 12.83% (mass) experimentally (calculated 12.54% (mass)).
Starting from about 2000C, the anhydrous coordination compound decomposes, which is accompanied by an endothermic effect with a maximum at a temperature of 423.90C. In the derivatogram at temperatures of 475, 552.6, and 578.50C, shallow but sharply defined endo-thermic effects are observed with insignificant weight losses of 9.61, 1.32, 0.57%, respectively, which could not be identified. In these
processes, the total weight loss of the organic part of the molecule is 44.20% experimentally (calculated 43.41%) without two oxygen atoms. The final product of thermolysis is NiO and this is experimentally 25.91% (mass) (calculated 27.09% (mass)).
Thermal decomposition of Ni coordination compound with pyromellitic acid:
[Ni2C6H2(COO)4 (H20)4] (H20)2 5 W161.9°C
-4H20
Ni2C6H2(COO)4
tmax111.7°C -2.5H2O *
tmax423-9 C
-organic part
№C6H2(COOV(H2O)4]
• 2NiO
Fig.4. Inferred schematic structure {[Ni2C6H2(COO)4(H2O)4] (H2O)2.5}n
of the two-dimensional coordination polymer
Thus, according to the results of the carried out studies, the coordination of each central atom includes four oxygen atoms of two carboxyl groups in terms of the chelate type and two oxygen atoms of two water molecules, and thus, the coordination number of nickel is 6, and the coordination polyhedron of nickel is an octahedron.
The inferred schematic structure of the two-dimensional polymer layer of the coordination polymer is given below (Figure 4).
Thus, the complex compound obtained from interaction of pyromellitic acid with nickel ion consists of two-dimensional 2D polymer layers. The water molecules are located in the space between two-dimensional layers forming networks of hydrogen bonds between them and bind them together. As a result of that the 2D polymer structure is restructured to a new 3D supramolecular formation [20].
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PÍROMELLÍT TURSUSU ÍLO NÍKELÍN KOMPLEKS BÍRLO§MOSÍ OSASINDA SUPRAMOLEKULYAR
NANOQURULUSLU KOORDÍNASÍON POLYMER
M.K.Mun$iyeva, F.B.OIiyeva, S.R.Mammadova, P.S. Safarova., M.M. Hasanova, B.T.Usubaliyev
ikinüvali masamali quruluçlu {[Ni2C6H2(COO)4(H2O)4]H2O2,5}n supramolekulyar birlaçma sintez edilmiçdir. Element, rentgen, ÍQ-spektroskopik va differensial termiki analizlarin naticalarina asasan kompleksin kimyavi formulu va quruluçu müayyan edilmiçdir. Difraksiya ayrilarinin identifikasiya edilmasi ila elementar qafas parametrlari tayin edilmiç va bu seriyadan olan tadqiq edilmiç bütün kompleks birlaçmalar ûçûn bünövra taçkil edan kompleks polimerin ikiôlçûlû polimer tabaqasinin sxematik quruluçu verilmiçdir. Kompleksda tabaqalar bir-biri ila birlaçir va hidrogen
rabitasinin istiqamatindan asili olaraq bir-birina nisbatan yer dayi§dirir va bu da elementar qafasin parametrlarinin dayi§masina gatirib gixarir. Belalikla, iki ölgülü polimer 2D tabaqalari 3D supramolekulyar qurulu§a gevrilir.
Agar sözlar: kompleks birla§ma, kompleks polimer, hidrogen rabitasi, 2D-qurulu§, 3D-qurulu§, iQ-spektri, termal pargalanma, supramolekul.
СУПРАМОЛЕКУЛЯРНЫЙ НАНОСТРУКТУРНЫЙ КООРДИНАЦИОННЫЙ ПОЛИМЕР НА ОСНОВЕ КОМПЛЕКСА НИКЕЛЯ С ПИРОМЕЛЛИТОВОЙ КИСЛОТОЙ
М.К.Муншиева, Ф.Б.Алиева, С.Р.Мамедова, Сафарова П.С, Гасанова, Б.Т.Усубалиев
Синтезирован биядерный комплекс {[Ni2C6H2(COO)4(H2O)4]-H2O2,5}n, обладающий супрамолекулярной структурой. Методами элементного, рентгенографического, ИК-спектроскопического и дифференциально-термического анализов изучены состави строение комплекса. Идентификацией дифрактограммы определены параметры элементарной ячейки и дана предполагаемая схематическая структура двухмерного полимерного слоя координационного полимера, который является строительным блоком для всех изученных комплексов из этой серии. Слои между собой связываются и смещаются относительно друг друга в зависимости от направленности водородных связей и это приводит к изменению параметров элементарной ячейки. Таким образом, двухмерные полимерные слои (2D) переходят в 3D супрамолекулярную структуру.
Ключевые слова: комплексное соединение, координационный полимер, водородная связь, 2D структура, 3D структура, ИК-спектр, термическая деструкция, супрамолекула.
