Nano-Ölçekli Olarak 4,5-Diklorftalik Asit Metal Komplekslerinin Hazırlanması ve Elektronik Özellikler

Yıl 2020, Cilt: 10 Sayı: 3, 1865 - 1875, 01.09.2020

Mehmet Salih Keskin Ümit Yıldıko , Derya Güngördü Solğun , Mehmet Salih Ağırtaş

https://doi.org/10.21597/jist.689109

Öz

Burada asit fonksiyonlu ftalik asit metal kompleksleri sentezlendi. Yapı analizi için Fourie dönüşümü kızılötesi spektroskopisi (FT-IR), X-ışını kırınım analizi (XRD), Taramalı elektron mikroskopisi-Enerji Dağıtıcı Spektrometresi (SEM + EDS) cihazları kullanılmıştır. 4,5-diklorftalik asidin bakır ve çinko komplekslerinin yapısal parametreleri, B3LYP yönteminin LanL2DZ baz seti ile belirlenmiştir. HOMO (en yüksek işgal edilen moleküler orbital) ve LUMO (en düşük işgal edilmeyen moleküler orbital) enerjileri ve elektron yoğunluk dağılım potansiyeli (MEP) gibi elektronik özellikler elde edildi. Hiperkonjugatif etkileşimlerden kaynaklanan moleküllerin stabilitesi, yük delokalizasyonu, doğal bağ orbital (NBO) analizi kullanılarak analiz edildi. Zn ve Cu-4,5-diklorftalik asidin (DCPA) teorik ve deneysel FT-IR spektrumlarının karşılaştırılması yapıldı ve Cu için R = 0.97204 ve Zn kompleksi için R = 0.97929 doğrusal çalışmalar formunda bulundu. İki karakterizasyon sonucunun tutarlı olduğu bulunmuştur.

Anahtar Kelimeler

Ftalik asit türevi, sentez, metal, elektronik özellikler

Preparation of Metal Complexes of 4,5-Dichlorphthalic Acid as Nanoscale and Electronic Properties

Öz

Here phthalic acid metal complexes with acid function were synthesized. Fourie transform infrared spectroscopy (FT- IR), X-ray diffraction analysis (XRD), Scanning electron microscopy-Energy Dispersive Spectrometry (SEM+EDS) devices were used for structure analysis. The structural parameters of the copper and zinc complexes of 4,5-dichlorphthalic acid were determined by the LanL2DZ basis base set of B3LYP method. Electronic properties such as HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies and molecular electrostatic potential (MEP) were obtained. Stability, charge delocalization of molecules resulting from hyperconjugative interactions were analyzed using natural bond orbital (NBO) analysis. The comparison of the theoretical and experimental FT-IR spectra of Zn and Cu-4,5-dichlorphthalic acid (DCPA) were made and R = 0.97204 for Cu and R = 0.97929 for Zn complex were found in linear fit studies. Two characterization results were found to be consistent.

Anahtar Kelimeler

Phthalic acid derivative, synthesis, metal, electronic properties

Kaynakça

• Cabir B, Yildiko, U, Ağirtaş, MS. (2019). Synthesis, DFT analysis, and electronic properties of new phthalocyanines bearing ETAEO substituents on peripheral position. Journal of Coordination Chemistry, 72(17): 2997-3011.
• Cabir B, Yildiko, U, Ağırtaş, MS, Horoz, S. (2020). Computational DFT calculations, photovoltaic properties and synthesis of (2R, 3S)-2, 3, 4-trihydroxybutoxy substituted phthalocyanines. Inorganic and Nano-Metal Chemistry, 50 (9): 816-827.
• Demir P, Akman, F. (2017). Molecular structure, spectroscopic characterization, HOMO and LUMO analysis of PU and PCL grafted onto PEMA-co-PHEMA with DFT quantum chemical calculations. Journal of Molecular Structure, 1134: 404-415.
• Detsri E, Seeharaj, P. (2017). Colorimetric detection of glutathione based on phthalic acid assisted synthesis of silver nanoparticles. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 533: 125-132.
• El Bourakadi K, El Mehdi Mekhzoum, M, Boeré, RT, El Kacem Qais, A, Bouhfid, R. (2019). Synthesis, characterization and DFT studies of 6-bis(2-(thiazol-4-yl)-benzimidazol-1-yl)hexane hemihydrate crystal: Experimental and theoretical investigation. Journal of Molecular Structure, 1202: 127253.
• Eşme A, Sağdınç, SG. (2017). Spectroscopic (FT–IR, FT–Raman, UV–Vis) analysis, conformational, HOMO-LUMO, NBO and NLO calculations on monomeric and dimeric structures of 4–pyridazinecarboxylic acid by HF and DFT methods. Journal of Molecular Structure, 1147: 322-334.
• Henglein A, Giersig, M. (1999). Formation of Colloidal Silver Nanoparticles:  Capping Action of Citrate. The Journal of Physical Chemistry B, 103(44): 9533-9539.
• Jayaprakash A, Arjunan, V, Jose, SP, Mohan, S. (2011). Vibrational and electronic investigations, thermodynamic parameters, HOMO and LUMO analysis on crotonaldehyde by ab initio and DFT methods. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 83(1): 411-419.
• Khajehzadeh M, Moghadam, M. (2017). Molecular structure, FT IR, NMR, UV, NBO and HOMO–LUMO of 1-(3-(dimethylamino)propyl)-1-(4-fluorophenyl)-1,3-dihydroisobenzofuran-5-carbonitrile by DFT/B3LYP and PBEPBE methods with LanL2DZ and 6-311++G(d,2p) basis sets. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 180: 51-66.
• Kumar S, Radha, A, Kour, M, Kumar, R, Chouaih, A, Pandey, SK. (2019). DFT studies of disubstituted diphenyldithiophosphates of nickel(II): Structural and some spectral parameters. Journal of Molecular Structure, 1185: 212-218.
• Liu H, Zhou, Y, Huang, H, Feng, Y. (2011). Phthalic acid modified TiO2 and enhanced photocatalytic reduction activity for Cr(VI) in aqueous solution. Desalination, 278(1): 434-437.
• Liu L-C, Xing, F, Bai, Y, Shao, M, Li, M, Zhu, S. (2014). Synthesis, structure, thermal stability and luminescence of five 2D coordination polymers based on 4-(4-oxypyridinium-1-yl) phthalic acid and transition metal ions. Journal of Molecular Structure, 1067: 74-82.
• Mathammal R, Monisha, NR, Yasaswini, S, Krishnakumar, V. (2015). Molecular structure, vibrational analysis (FT-IR, FT-Raman), NMR, UV, NBO and HOMO–LUMO analysis of N,N-Diphenyl Formamide based on DFT calculations. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 139: 521-532.
• Mıhçıokur Ö, Özpozan, T. (2017). Molecular structure, vibrational spectroscopic analysis (IR & Raman), HOMO-LUMO and NBO analysis of anti-cancer drug sunitinib using DFT method. Journal of Molecular Structure, 1149: 27-41.
• Pandey M, Muthu, S, Nanje Gowda, NM. (2017). Quantum mechanical and spectroscopic (FT-IR, FT-Raman,1H,13C NMR, UV-Vis) studies, NBO, NLO, HOMO, LUMO and Fukui function analysis of 5-Methoxy-1H-benzo[d]imidazole-2(3H)-thione by DFT studies. Journal of Molecular Structure, 1130: 511-521.
• Prabhaharan M, Prabakaran, AR, Gunasekaran, S, Srinivasan, S. (2015). DFT studies on vibrational spectra, HOMO–LUMO, NBO and thermodynamic function analysis of cyanuric fluoride. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 136: 494-503.
• Priya MK, Revathi, BK, Renuka, V, Sathya, S, Asirvatham, PS. (2019). Molecular Structure, Spectroscopic (FT-IR, FT-Raman, 13C and 1H NMR) Analysis, HOMO-LUMO Energies, Mulliken, MEP and Thermal Properties of New Chalcone Derivative by DFT Calculation. Materials Today: Proceedings, 8: 37-46.
• Rawat KA, Singhal, RK, Kailasa, SK. (2017). One-pot synthesis of silver nanoparticles using folic acid as a reagent for colorimetric and fluorimetric detections of 6-mercaptopurine at nanomolar concentration. Sensors and Actuators B: Chemical, 249: 30-38.
• Rocha M, Di Santo, A, Arias, JM, Gil, DM, Altabef, AB. (2015). Ab-initio and DFT calculations on molecular structure, NBO, HOMO–LUMO study and a new vibrational analysis of 4-(Dimethylamino) Benzaldehyde. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 136: 635-643.
• Saravanan RR, Seshadri, S, Gunasekaran, S, Mendoza-Meroño, R, Garcia-Granda, S. (2014). Crystallographic, experimental (FT-IR and FT-RS) and theoretical (DFT) investigation, UV–Vis, MEP, HOMO–LUMO and NBO/NLMO of (E)-1-[1-(4-Chlorophenyl)ethylidene]thiosemicarbazide. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 121: 268-275.
• Solğun DG, Keskin, MS, Yıldıko, Ü, Ağırtaş, MS. (2020). DFT analysis and electronic properties, and synthesis of tetra (9-phenyl-9H-xanthen-9-yl) oxy peripheral-substituted zinc phthalocyanine. Chemical Papers, 74: 2389-2401.
• Srivastava AK, Pandey, AK, Jain, S, Misra, N. (2015). FT-IR spectroscopy, intra-molecular C−H⋯O interactions, HOMO, LUMO, MESP analysis and biological activity of two natural products, triclisine and rufescine: DFT and QTAIM approaches. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 136, 682-689.
• Vennila P, Govindaraju, M, Venkatesh, G, Kamal, C. (2016). Molecular structure, vibrational spectral assignments (FT-IR and FT-RAMAN), NMR, NBO, HOMO-LUMO and NLO properties of O-methoxybenzaldehyde based on DFT calculations. Journal of Molecular Structure, 1111: 151-156.