INVESTIGATION OF PHYSICAL AND CHEMICAL PROPERTIES OF 2-[(2-HYDROXY-4-NITROPHENYL)AMINOMETHYLENE]-CYCLOHEXA-3,5-DIEN-1(2H)-ONE BY DFT METHOD

Yıl 2015, Sayı: 2015 Özel Sayısı, 109 - 126, 15.01.2016

Cem Cüneyt Ersanlı , Başak Koşar

Öz

This work presents the characterization on the
tautomeric forms of 2-[(2-hydroxy-4-nitrophenyl)aminomethylene]cyclohexa-3,5-dien-1(2H)-one, (I), quantum chemical calculations. The tautomeric forms of I in gas-phase and various solvents
have been defined at the B3LYP/6-311+G(d,p) level of density functional theory
(DFT). DFT calculations of non-linear optical (NLO) properties, natural bond
orbital (NBO) analysis, frontier molecular orbitals (FMOs), molecular
electrostatic potential (MEP) and thermodynamic properties with temperature
ranging from 100 K to 300 K have been have been defined at the same level of
theory. In addition, Mulliken population analysis of I have been performed at B3LYP/6-31(d) level of DFT. 

Anahtar Kelimeler

Schiff base, tautomeric form, DFT, MEP

YFT METODUYLA 2-[(2-HİDROKSİ-4-NİTROFENİL)AMİNOMETİLEN]SİKLOHEKSA-3,5-DİYEN-1(2H)-ON’UN FİZİKSEL VE KİMYASAL ÖZELLİKLERİNİN ARAŞTIRILMASI

Öz

Bu çalışmada
tautomerik formlardaki 2-[(2-hidroksi-4-nitrofenil)aminometilen]siklohekza-3,5-diyen-1(2H)-on (I)’un kuantum kimyasal heasaplamalar ile karakterizasyonu
sunulmaktadır. Gaz fazında ve çeşitli çözücü fazlarında bileşiğin tautomerik
formları B3LYP/6-311+G(d,p) teori seviyesinde yoğunluk fonksiyonel teori (YFT)
ile belirlenmiştir. Doğrusal-olmayan optik özellikleri, doğal bağ orbital
analizi, sınır moleküler orbitalleri, moleküler elektrostatik potansiyel (MEP)
ve 100 K ile 300 K arasındaki sıcaklık aralığında termodinamik özellikleri
yoğunluk fonksiyonel teori ile aynı baz setinde hesaplanmıştır. Bunlara ek
olarak, bileşiğin Mulliken populasyon analizi B3LYP/6-31(d) teori seviyesinde
YFT hesaplamaları ile gerçekleştirilmiştir. 

Anahtar Kelimeler

Schiff bazı, tautomerik form, YFT, MEP

Kaynakça

• [1] M. D. Cohen, G. M. J. Schmidt, and S. Flavian, “Experiments on photochromy and thermochromy of crystalline anils of salicylaldehydes”, J. Chem. Soc., 2041-2051 (1964).
• [2] H. S. Maslen, and T. N. Waters, “The conformation of Schiff-base complexes of copper(II)”, Coord. Chem. Rev., 17, 137-176 (1975).
• [3] J. M. Stewart, and E. C. Lingafelter, “The crystal structure of bis-salicylaldiminato-nickel(II) and -copper(II)”, Acta Cryst., 12, 842-845 (1959).
• [4] E. Hadjoudis, M. Vitterakis, and I. Moustakali-Mavridis, “Photochromism and thermochromism of schiff bases in the solid state and in rigid glasses”, Tetrahedron, 43, 1345-1360 (1987).
• [5] I. Moustakali-Mavridis, E. Hadjoudis, and A. Mavridis, “Crystal and Molecular Structure of Thermochromic Schiff Bases II. Structures of N-salicylidene-3-aminopyridine and N- (5-methoxy-salicylidene)-3-aminopyridine”, Acta Cryst., B36, 1126-1130 (1980).
• [6] P. M. W. Gill, B. G. Johnson, J. A. Pople, and M. J. Frisch, “The performance of the Becke-Lee-Yang-Parr (BLYP) density functional theory with various basis sets”, Chem. Phys. Lett., 197, 499-505 (1992).
• [7] C. C. Ersanli, Ç. Albayrak, M. Odabaşoğlu, and A. Erdönmez, “2-[(2-Hydroxy-4-nitrophenyl)aminomethylene]-cyclohexa-3,5-dien-1(2H)-one”, Acta Cryst., C59, 601-602 (2003).
• [8] A. D. Becke, “Density‐functional thermochemistry. III. The role of exact exchange”, J. Chem. Phys., 98, 5648-5652 (1993).
• [9] M. J. Frisch et al., Gaussian 03, Gaussian, Inc., Wallingford, CT, (2004).
• [10] R. Dennington II, T. Keith, and J. Milliam, GaussView, Version 4.1.2. Semichem Inc., Shawnee Mission, KS, (2007).
• [11] S. Miertus, E. Scrocco, and J. Tomasi, “Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects”, J. Chem. Phys., 55, 117-129 (1981).
• [12] V. Barone and M. Cossi, J. Phys. Chem. A102, 1995-2001 (1998).
• [13] E. D. Glendening, A. E. Reed, J. E. Carpenter, and F. Weinhold, NBO Version 3.1, CI, University of Wisconsin, Madison, 2003.
• [14] I. Moustakali-Mavridis, E. Hadjoudis, and A. Mavridis, “Crystal and Molecular Structure of Some Thermochromic Schiff Bases”, Acta Cryst., B34, 3709-3715 (1978).
• [15] A. Masternak, G. Wenska, J. Milecki, B. Skalski, and S. Franzen, “Solvatochromism of a Novel Betaine Dye Derived from Purine”, J. Phys. Chem. A109, 759-766, (2005).
• [16] Y.Le and J.F. Chen, M.Pu, “Electronic structure and UV spectrum of fenofibrate in solutions”, Int. J. Pharm. Sci., 358, 214-218 (2008).
• [17] S. L. Guo, T. P. Li, T. B. Wang, Z. S. Liu, and T. D. Cao, “Third-order nonlinearities and optical limiting properties of complex Co2L3”, Opt. Mater., 29, 494-498 (2007).
• [18] K. S. Thanthiriwatte, and K. M. Nalin de Silva, “Non-linear optical properties of novel fluorenyl derivatives-ab initio quantum chemical calculations”, J. Mol. Struct., 617, 169-175 (2002).
• [19] Y. X. Sun, Q. L. Hao, Z. X. Yu, W. X. Wei, L. D. Lu, and X. Wang, “Experimental and density functional studies on 4-(4-cyanobenzylideneamino)antipyrine”, Mol. Phys., 107, 223-235 (2009).
• [20] R. Zhang, B. Du, G. Sun, and Y. Sun, “Experimental and theoretical studies on o-, m- and p-chlorobenzylideneaminoantipyrines”, Spectrochim. Acta A75, 1115-1124 (2010).
• [21] F. Weinhold, and C. R. Landis, “Natural bond orbitals and extensions of localized bonding concepts”, Chem Educ. Res. Pract. Eur., 2, 91-104 (2001).
• [22] J. S. Murray, and K. Şen, Molecular Electrostatic Potentials, Concepts and Applications, Elsevier, Amsterdam, (1996).