Tereftalat ile [N-(2-Hidroksietil)-Etilendiamin] İçeren Karışık ligantlı Bakır(II) Kompleksinin Sentezi, Spektral, Termal ve Yapısal Karakterizasyonu

Yıl 2020, , 985 - 997, 01.06.2020

Tuğba Aycan , Hümeyra Paşaoğlu

https://doi.org/10.21597/jist.649334

Öz

[Cu(Hydet-en)2].(Tpht) (Tpht=Tereftalik asit dianyonu, Hydet-en=N-(2-hidroksietil)etilendiamin) kompleksi sentezlenmiştir. Kompleks tek kristal X-ışını tayini, FT-IR spektroskopisi, UV-Vis spektroskopisi, termogravimetrik analiz ve elementel analiz ile karakterize edilir. Her bir hydet-en ligandı bakır metaline iki dişli olarak koordine olurken, tpht2- anyonu ise birim hücrede serbest olarak bulunmaktadır. Bakır merkezi düzgün bir kare düzlem geometriye sahiptir. Kare düzlem geometriye sahip kompleksin ekvatoral düzlemini hydet-en ligantlarının birincil ve ikincil amin grupları oluşturmaktadır. Monomerler O-H∙∙∙O ve N-H∙∙∙O hidrojen bağlarıyla bağlanarak supramoleküler yapıyı oluşturur. Kompleksin FT-IR araştırması, orta IR bölgesi içinde gerçekleştirildi. Esas olarak tereftalik asit ve N-(2-hidroksietil)etilendiamin) ligantlarının karakteristik titreşimleri göz önünde bulundurarak kompleksin titreşimlerine odaklanıldı. TG, DTA ve DTG teknikleri kullanılarak kompleksin termal davranışları izlenmiştir.

Anahtar Kelimeler

Tek Kristal XRD, FT-IR Spektroskopisi, Termogravimetrik Analiz, Tereftalik Asit, Elektronik Geçişler

Destekleyen Kurum

Ondokuz Mayıs Üniversitesi

Proje Numarası

PYO.FEN.1904.10.07

Teşekkür

Kristalografik dataların toplanmasında emeği geçen Öğr. Gör. Hakan BÜLBÜL'e teşekkür ederim.

Synthesis, Spectral, Thermal and Structural Characterization of Mixed ligand Copper(II) Complex Containing [N-(2-Hydroxyethyl)-Ethylenediamine] with Terephthalate

Öz

The complex [Cu(hydet-en)2].(tpht) synthesized is characterized by single crystal X-ray determination, FT-IR spectroscopy, UV-Vis spectroscopy, thermogravimetric analysis and elemental analysis (tpht=dianion of terephthalic acid, hydet-en=N-(2- hydroxyethyl)ethylenediamine). While each hydet-en ligand coordinates to copper metal as bidentate, the tpht2-anion is freely available in the unit cell. Copper center has a square plane geometry. In the square geometry, the equatorial plane of the complex is composed of primary and secondary amine groups of hydet-en ligands. Monomers are bonded with O-H∙∙∙O and N-H∙∙∙O hydrogen bonds to form a supramolecular structure. FT-IR investigation of the complex was performed in the middle IR region. The vibrations of the complex were focused mainly considering the characteristic vibrations of terephthalic acid and N-(2- hydroxyethyl)ethylenediamine ligands. Thermal behaviour of the complex was followed using TG, DTA and DTG techniques.

Anahtar Kelimeler

Single Crystal XRD, FT-IR spectroscopy, Thermogravimetric Analysis, Terephthalic Acid, Electronic Transitions

Proje Numarası

PYO.FEN.1904.10.07

Kaynakça

• Al-Hashemi R, Safari N, Amani S, Amani V, Abedi A, Reza Khavasi H, Weng Ng S, 2010. Synthesis, characterization, and crystal structure determination of two copper (II) complexes:[Cu (dm4bt) Cl2 (DMSO)] and [{Cu (dm4bt)(H2O)(tpht)}· H2O] n. Journal of Coordination Chemistry, 63(18): 3207-3217.
• Álvarez L, Grirrane A, Moyano R, Álvarez E, Pastor A, Galindo A, 2010. Comparison of the coordination capabilities of thiodiacetate and oxydiacetate ligands through the X-ray characterization and DFT studies of [V(O)(tda)(phen)]·4H2O and [V(O)(oda)(phen)]·1.5H2O. Polyhedron, 29(16): 3028-3035.
• Choubey S, Roy S, Bhar K, Ghosh R, Mitra P, Lin C-H, Ribas J, Ghosh BK, 2013. Syntheses, structures, and magnetic properties of terephthalato bridged dinuclear copper(II) and manganese(II) complexes with a tetradentate N-donor Schiff base. Polyhedron, 55: 1-9.
• Etter MC, 1990. Encoding and decoding hydrogen-bond patterns of organic compounds. Accounts of chemical research, 23(4): 120-126.
• Farrugia LJ, 1997. ORTEP‐3 for Windows‐a version of ORTEP‐III with a Graphical User Interface (GUI). Journal of Applied Crystallography, 30(5‐1): 565-565.
• Farrugia LJ, 1999. WinGX suite for small‐molecule single‐crystal crystallography. Journal of Applied Crystallography, 32(4): 837-838.
• Feng S, Xu R, 2001. New materials in hydrothermal synthesis. Accounts of chemical research, 34(3): 239-247.
• Férey G, 2001. Microporous solids: From organically templated inorganic skeletons to hybrid frameworks... ecumenism in chemistry. Chemistry of materials, 13(10): 3084-3098.
• Golovanov I, Zhenodarova S, 2006. Quantitative structure-property relationship: XXVI. Toxicity of aliphatic carboxylic acids. Russian journal of general chemistry, 76(1): 40-44.
• Grirrane A, Pastor A, Mealli C, Ienco A, Rosa P, Prado-Gotor R, Galindo An, 2004. Synthesis, structure, magnetic and electrochemical properties of an oxydiacetate iron(II) complex. Inorganica Chimica Acta, 357(14): 4215-4219.
• Han L, Sakamoto Y, Terasaki O, Li Y, Che S, 2007. Synthesis of carboxylic group functionalized mesoporous silicas (CFMSs) with various structures. Journal of Materials Chemistry, 17(12): 1216-1221.
• Johnston LL, Nettleman JH, Braverman MA, Sposato LK, Supkowski RM, LaDuca RL, 2010. Copper benzenedicarboxylate coordination polymers incorporating a long-spanning neutral co-ligand: Effect of anion inclusion and carboxylate pendant-arm length on topology and magnetism. Polyhedron, 29(1): 303-311.
• Karadag A, Bulut A, Senocaky A, Uçar İ, Bueyuekguengoerz O, 2007. Preparations, IR spectra and crystal structures of cyano-bridged bimetallic complexes of zinc (II) and cadmium (II) with tetracyanopalladate (II). Journal of Coordination Chemistry, 60(19): 2035-2044.
• Karadag A, Pasaoglu H, Kastas G, Büyükgüngör O, 2005. Synthesis, IR spectrum, thermal behaviour and crystal structure of a novel one-dimensional cyano-bridged zinc(II)/nickel(II) complex. Zeitschrift für Kristallographie - Crystalline Materials, 220(1): 74.
• Karthikeyan N, Joseph Prince J, Ramalingam S, Periandy S, 2015. Electronic [UV–Visible] and vibrational [FT-IR, FT-Raman] investigation and NMR–mass spectroscopic analysis of terephthalic acid using quantum Gaussian calculations. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 139: 229-242.
• Li X, Wang R, Zhao H, Wu B, 2016. Co−MOFs with 1,1′-(5-methyl-1,3-phenylene)bis(1H-imidazole) and aromatic carboxylates as coligands: synthesis, structure, and spectroscopic and thermal characterizations. Journal of Coordination Chemistry, 69(15): 2247-2262.
• Liu B, Hu W, Robertson GP, Guiver MD, 2008. Poly (aryl ether ketone) s with carboxylic acid groups: synthesis, sulfonation and crosslinking. Journal of Materials Chemistry, 18(39): 4675-4682.
• Luttrell WE, Hester RL, 2016. Terephthalic acid. Journal of Chemical Health and Safety, 23(6): 49-52.
• Mahalakshmi R, Raman N, 2013. Enthused research on DNA-binding and DNA-cleavage aptitude of mixed ligand metal complexes. Spectrochim Acta A Mol Biomol Spectrosc, 112: 198-205.
• Malaestean Y, Filippova IG, Ellern A, Simonov YA, Baca SG, 2008. Supramolecular architecture of the [M(1-MeIm)2(H2O)4]2+ (M = Ni, Co) complexes with the terephthalate anion. Russian Journal of Coordination Chemistry, 34(5): 334-338.
• Mautner FA, Vicente R, Louka FRY, Massoud SS, 2008. Dinuclear fumarato- and terephthalato-bridged copper(II) complexes: Structural characterization and magnetic properties. Inorganica Chimica Acta, 361(5): 1339-1348.
• Nishida Y, Kida S, 1979. Splitting of d-orbitals in square planar complexes of copper (II), nickel (II) and cobalt (II). Coordination Chemistry Reviews, 27(3): 275-298.
• Panina N, Belyaev A, Simanova S, 2002. Carboxylic acids and their anions. Acid and ligand properties. Russian journal of general chemistry, 72(1): 91-94.
• Sheldrick GM, 2008. A short history of SHELX. Acta Cryst. A: Found Adv., 64(1): 112-122.
• Shi Z, Li L, Niu S, Jin J, Chi Y, Zhang L, Liu J, Xing Y, 2011. A series of dn transition metal coordination complexes: Structures and comparative study of surface electron behaviors (n=9, 8, 7, 6, 5). Inorganica Chimica Acta, 368(1): 101-110.
• Spek AL, 2009. Structure validation in chemical crystallography. Acta Crystallographica Section D: Biological Crystallography, 65(2): 148-155.
• Stoe, Cie X, 2002. Area (Version 1.18) and X-Red32 (Version 1.04). Stoe&Cie, Darmstadt, Germany.
• Willett RD, Liles Jr O, Michelson C, 1967. Electronic absorption spectra of monomeric copper (II) chloride species and the electron spin resonance spectrum of the square-planar CuCl42-ion. Inorganic Chemistry, 6(10): 1885-1889.
• Yang L, Powell DR, Houser RP, 2007. Structural variation in copper (I) complexes with pyridylmethylamide ligands: structural analysis with a new four-coordinate geometry index, τ 4. Dalton Transactions(9): 955-964.
• Yang LN, Zhou CH, Zhi YX, Hei JH, Li J, Zhang FX, 2013. pH-dependent syntheses and crystal structures, characterizations, and DFT calculations of complexes with 2,2′-biimidazole and terephthalic acid ligands. Russian Journal of Coordination Chemistry, 39(8): 620-627.
• Zou Z, Chung B, Nguyen T, Mentone S, Thomson B, Biemesderfer D, 2004. Linking receptor-mediated endocytosis and cell signaling evidence for regulated intramembrane proteolysis of megalin in proximal tubule. Journal of Biological Chemistry, 279(33): 34302-34310.