SYNTHESIS, EXPERIMENTAL AND THEORETICAL CHARACTERIZATION OF N,N'-DİACETYL-1,13-DİAZA-24-CROWN-8

Yıl 2013, Cilt: 8 Sayı: 1, 11 - 23, 01.02.2013

Metin Koparır

Öz

This work presents the characterization of N,N'-diacetyl-1,13-diaza-24-crown-8 (I) by quantum chemical calculations and spectral techniques. The molecular geometry and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of I in the ground state have been calculated using the density functional method (B3LYP) with the 6â'31G(d,p) basis set. The calculated results show that the optimized geometry can well reproduce the crystal structure, and the theoretical chemical shift values show good agreement with experimental values. The predicted non-linear optical properties of I are greater than ones of urea. In addition, DFT calculations of molecular electrostatic potentials and frontier molecular orbitals of I were carried out at the B3LYP/6â'31G(d,p) level of theory.

Anahtar Kelimeler

N, N'-diacetyl-1, 13-diaza-24-crown-8, DFT, NMR, Single-crystal X-ray study, MEP,

N,N'-DİASETİL-1,13-DİAZA-24-CROWN-8'İN SENTEZİ, DENEYSEL VE TEORİK KAREKTERİZASYONU

Öz

Bu çalışma da N,N'-diasetil-1,13-diaza-24-crown-8'in spektral teknikler ve kimyasal hesaplamalar ile karakterizasyonu sunulmaktadır. Molekülün geometrisi, 1H ve 13C kimyasal kayma değerleri yoğunluk fonksiyon metoduna (B3LYP) göre 6-31G(d,p) seti kullanılarak temel halde hesaplanmıştır. Hesaplanan optimize yapı ve kimyasal kayma değerleri deneysel sonuçlar ile iyi bir uyum içerisindedir. Molekülün doğrusal olmayan optik özellikleri üre'ye göre daha büyüktür. Bunlara ek olarak, moleküler elektrostatik potansiyel (MEP) ve sınır moleküler orbitaller B3LYP/6-31G(d,p) teori seviyesinde DFT hesaplamaları ile gerçekleştirilmiştir.

Anahtar Kelimeler

N, N'-diasetil-1, 13-diaza-24-crown-8, DFT, NMR, Single-kristal X-ışını çalışması, MEP,

Kaynakça

• Melson, G.A., (1979). Coordination Chemistry of Macrocyclic Compounds. New York: Plenum Publishing Corp.
• Formanowskii, A.A. and Mikhura, I.V., (1997). Synthesis of Macrocyclic Compounds. In Macrocyclic Compounds in Analytical Chemistry. New York: Wiley- Interscience.
• Chartres, J.D., Davies, M.S., Lindoy, L.F., Meehan, G.V., and Wei, G., (2006). Macrocyclic Ligand Design: The Interaction of Selected Transition and Post-Transition Metal Ions With a 14- Membered N2S2-Donor Macrocycle. Inorganic Chemistry Communications, Volume:2006, pp.:751-754.
• Proft, F.D. and Geerlings, P., (2001). Conceptual and computational DFT in the study of aromaticity. Chemical Reviews, Volume:101, pp.:1451-1464.
• Orek, C., Koparir, P., and Koparir, M., (2012). N-Cyclohexyl-2- [5-(4-pyridyl)-4-(p-tolyl)-4H-1,2,4-triazol-3-ylsulfanyl]- acetamide dihydrate:Synthesis, experimental, theoretical characterization and biological activities. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume:97, pp.:923-934.
• Cansiz, A., Cetin, A., Orek, C., Karatep, M., Sarac, K., Kus, A., and Koparir, P., (2012). 6-Phenyl-3-(4-pyridyl)-1,2,4- triazolo-[3,4-b][1,3,4]thiadiazole: Synthesis, experimental, theoretical characterization and biological activities. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume:97, pp.:607-615.
• Tanak, H., (2011). DFT computational modeling studies on 4-(2,3- Dihydroxybenzylideneamino)-3-methyl-1H-1,2,4-triazol-5(4H)-one. Computational And Theoretical Chemistry, Volume:967, pp: 93-101
• Andzelm, J. and Fitzgerald, G., (1991). Chemical Applications of Density Funtional Theory - Comparison to Experiment, Hartree- Fock, and Perturbation-Theory. Journal of Physical Chemistry, Volume:95, pp:10531-10534
• Andzelm, J. and Wimmer, E., (1992). Density Functional Gaussian- Type-Orbital Approach to Molecular Geometries, Vibrations, and Reaction Energies. Journal of Chemical Physics, Volume:96, pp:1280-1303
• Jeffrey, C.B., Alan, P.M., and Hazlewood, A., (2000). N,N’- Diacetyl-1,13-diaza-24-crown-8. Acta Crystallographica Section E Structure Reports Online, Volume:E57, pp.:13-15.
• Schlegel, H.B., (1982). Optimization of Equilibrium Geometries and Transition Structure. Journal of Computional Chemistry, Volume:3, pp:214-218
• Peng, C., Ayala, P.Y., and Schlegel, H.B., (1996). Using Redundant Internal Coordinates to Optimize Equilibrium Geometries and Transition States. Journal of Computational Chemistry, Volume:17, pp:49-56
• Bryan, J.C., Lavis, J.M., Hay, B.P., and Sachleben, R.A., (2000). N-ethylazatribenzo-21-crown-7. Acta Crystallographica Section C-Crystal Structure Communications, Volume:56, pp.:391- 392.
• Bryan, J.C., Bunick, G.J., and Sachleben, R.A., (1999). Tetrabenzo-24-crown-8. Acta Crystallographica Section C-Crystal Strusture Communications, Volume:55, pp.:250-252.
• Tanak, H., (2011). Crystal Structure, Spectroscopy, and Quantum Chemical Studies of €-2[(2-Chlorophenyl)iminomethyl]-4- trifluoromethoxyphenol. Journal of Physical Chemistrya, Volume:115, pp.:13865-13876
• Politzer, P. and Murray, J.S., (1991). Theoretical biochemistry and molecular biophysics: a comprehensive survey. Adenine Press, Schenectady, NY.
• Politzer, P. and Murray, J.S., (2002). The Fundamental Nature and Role of the Electorstatic Potential in Atoms and Molecules. Theoretical Chemistry Acoounts, Volume:108, pp.: 134.
• Amalanathan, M., Rastogi, V.K., Joe, I.H., Palafox, M.A., and Tomar, R., (2009). Density functional theory calculations and vibrational spectral analysis of 3,5-(dinitrobenzoic acid). Spevtrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, Volume:78, pp.:1437-1444.
• Padmaja, L., Ravikumar, C., Sajan, D., Joe, I.H., Jayakumar, V.S., Pettit, G.R., ans Nielsen, O.F., (2009). Density Functional Study on the Structural Conformations and Intramolecular Charge transfer From the Vibrational Spectra of the Anticancer Drug Combretastatin. Journal of Raman Spectroscopy, Volume:40, pp.:419-428.
• Sagdinc, S. and Pir, H., (2009). Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, Volume:73, pp.:181-187.
• Thanthiriwatte, K.S. and de Silva, K.M.N., (2002). Non-linear Optical Properties of Novel Fluorenyl Derivatives - ab Initio Quantum Chemical Calculations. Journal of Molecular Structure- Theochem, Volume:617, pp.:169-175.
• Maroulis, G., Begue, D., and Pouchan, C., (2003). Accurate Dipole Polarizabilities of Small Silicon Clusters From ab Initio and Density Functional Theory Calculations. Journall of Chemical Physics, Volume:119, pp.:794-798.
• Maroulis, G., (2008). How Large is the Static Electric (hyper)Polarizability Anisotropy in HXeI. Journal of Chemical Physics, Volume:129, pp.:044314-044321.
• Qin, C., Si, Y., Yang, G., and Su, Z., (2011). Quantum Chemical Study of Structures, Electronic Spectrum, and Nonlinear Optical Properties of Polynuclear Lithium Compounds. Computational and Theoretical Chemistry, Volume:966, pp.: 14-19.