Cis-2,6-bis(2-klorofenil)-3,3-dimetilpiperidin-4-one bileşiği üzerine yapısal, spektroskopik, elektronik ve doğrusal olmayan optiksel araştırmalar

Piperidin, heterosiklik moleküller arasında en iyi bilinen yapılardan biridir. Güncel çalışmalar bu tür bileşiklerin yapıdoğrusal olmayan optiksel performans ilişkisine odaklanmaktadır. Doğrusal olmayan optik malzemelerin fiber optik iletişim ve optik sinyal işlemlerinde hayati öneme sahip oldukları bilinmektedir. Bu çalışmada, bir piperidin türevi olan cis-2,6-bis(2-klorofenil)-3,3-dimetilpiperidin-4-one (2C3DMPO) bileşiğinin yapısal, spektroskopik, elektronik ve doğrusal olmayan optik özellikleri analiz edilmiştir. 2C3DMPO için elde edilen teorik sonuçlar deneysel değerler ile iyi bir uyum içindedirler. NMR spektrumunda, elektronegatif O atomundan dolayı, C4 atomu aşağı alanda sinyal vermiştir. HOMO ve LUMO arasındaki küçük enerji aralığı, bağ ve antibağ yörüngeleri arasındaki yoğun etkileşmeler yüksek doğrusal olmayan optik özelliklerin göstergesidir.

Structural, spectroscopic, electronic and nonlinear optical investigations on cis-2,6-bis(2-chlorophenyl)-3,3-dimethylpiperidin-4-one

Piperidine is one of the most recognizable structural entities among heterocyclic molecules. The current studies have been focused on structure-nonlinear optical performance relationship of such compounds. It is well known that the nonlinear optical materials play a vital role in the field of fiber optic communications and optical signal process. In this study, cis-2,6-bis(2-chlorophenyl)-3,3-dimethylpiperidin-4-one (2C3DMPO) compound which is a piperidine derivate has been analyzed in terms of structural, spectroscopic, electronic and nonlinear optical properties. Obtained theoretical results for 2C3DMPO are in good agreement with previously reported experimental data. In NMR calculations C4 atom gives signal at downfield region due to bonding electronegative O atom. The small energy gap between HOMO and LUMO energies, and the intensive interactions between the bonding and antibonding orbitals are indicators of high nonlinear optical properties.

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[1] [1] S. Balaprabhakaran, J. Chandrasekaran, B. Babu, R. Thirumurugan and K. Anitha, "Synthesis, crystal growth and physiochemical characterization of organic NLO crystal: Lornithinium dipicrate (LODP)." Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 136, pp 700-706, 2015.
[2] R.N. Rai, Shiva Kant, R.S.B. Reddi, S. Ganesamoorthy and P.K. Gupta, "Solid state synthesis, crystal growth and optical properties of urea and p-chloronitrobenzene solid solution." Journal of Solid State Chemistry, vol. 233, pp 244-251, 2016.
[3] Ö. Tamer, N. Dege, D. Avcı, Y. Atalaya, İ.Ö. İlhan and Mehmet Çadır, "Synthesis, structural and spectroscopic evaluations and nonlinear optical properties of 3, 5-bis (4-methoxyphenyl)- 4, 5-dihydro-1H-pyrazole-1-carbothioic O-acid." Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 137, 1387- 1396, 2015.
[4] Ö. Tamer, N. Dege, G. Demirtaş, D. Avcı, Y. Atalay, M. Macit and S.Şahin, "Crystal structure and spectroscopic characterization of (E)-2-(((4- bromo-2-(trifluoromethoxy) phenyl) imino) methyl)-4-nitrophenol: A combined experimental and computational study." Journal of Molecular Structure, vol. 1063, pp 295-306, 2014.
[5] K. Parasuraman, K. Sakthi Murugesan, R. Uthrakumar, S. Jerome Das and B. Milton Boaz, "Growth, optical, mechanical and dielectric studies on NLO active pure and metal ion doped single crystals of bis-thiourea zinc chloride." Physica B, vol. 406, pp 3856-3860, 2011.
[6] Ö. Tamer, D. Avcı and Y. Atalay, "Synthesis, crystal structure, spectroscopic characterization and nonlinear optical properties of Co (II)- picolinate complex." Materials Chemistry and Physics, vol. 168, pp 138-146, 2015.
[7] Ö.Tamer, D. Avcı and Y.Atalay, "Synthesis, Xray structure, spectroscopic characterization and nonlinear optical properties of Nickel (II) complex with picolinate: A combined experimental and theoretical study." Journal of Molecular Structure, vol. 1098, pp 12-20, 2015.
[8] S. Altürk, Ö. Tamer, D. Avcı and Y. Atalay, "Synthesis, spectroscopic characterization, second and third-order nonlinear optical properties, and DFT calculations of a novel Mn (II) complex." Journal of Organometallic Chemistry, vol. 797, pp 110-119, 2015.
[9] S. Ponnuswamy, V. Mohanraj, S.S. Ilango, M. Thenmozhi and M.N. Ponnuswamy, "Growth, thermal, mechanical, structural and optical properties of organic NLO crystals of novel cis- 2, 6-bis (2-chlorophenyl)-3, 3- dimethylpiperidin-4-one." Journal of Molecular Structure, vol. 1081, pp 449-456, 2015.
[10] Gaussian 09, Revision D.01, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J.Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski and D.J. Fox, Gaussian, Inc., Wallingford CT, 2009.
[11] GaussView, Version 5, R. Dennington, T. Keith and J. Millam, Semichem Inc., Shawnee Mission, KS, 2009.
[12] A.D. Becke, "Density-functional thermochemistry. III. The role of exact exchange." The Journal of chemical physics, vol. 98, pp 5648-5652, 1993.
[13] C. Lee, W. Yang and R.G. Parr, "Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density." Physical review B, vol. 37, pp 785, 1988
[14] M.J. Frisch, J.A. Pople and J.S. Binkley, "Self- consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets." The Journal of chemical physics, vol. 80, pp 3265-3269, 1984.
[15] G. Scalmani, M. J. Frisch, B. Mennucci, J. Tomasi, R. Cammi and V. Barone, "Geometries and properties of excited states in the gas phase and in solution: Theory and application of a timedependent density functional theory polarizable continuum model." The Journal of chemical physics, vol. 124, pp 1-15, 2006.
[16] J.B. Foresman, in: E. Frisch (Ed.), Exploring Chemistry with Electronic Structure methods: A Guide to Using Gaussian, Gaussian Inc., Pittsburg, PA, 1996.
[17] Ö. Tamer, D. Avcı and Y. Atalay, "Quantum chemical characterization of N-(2- hydroxybenzylidene) acetohydrazide (HBAH): A detailed vibrational and NLO analysis." Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 117, pp 78-86, 2014.
[18] G. Varsanyi, Vibrational Spectra of Benzene Derivatives, Academic Press, New York, 1969.
[19] G. Varsanyi, Assignments for Vibrational Spectra of Seven Hundred Benzene Derivatives. Academic Kiaclo, Budapest, 1973.
[20] T. Schlick, Molecular Modeling Simulation: An Interdisciplinary Guide, second ed., Springer, New York, 2010.
[21] J. Tomasi, P. Politzer and D.G. Truhlar, Chemical applications of atomic and molecular electrostatic potentials. Plenum, New York, 1981.
[22] M. Perutz, "Electrostatic effects in proteins" Science, vol. 201, pp 1187-1191, 1978.
[23] M. Del Zoppo, C. Castiglioni, P. Zuliani, A. Razelli, G. Zerbi and M. Blanchard-Desce, "Use of vibrational spectra for the determination of first-order molecular hyperpolarizabilities of push-pull polyenes as function of structural parameters." Journal of applied polymer science, vol.70, pp 1311-1320, 1998.
[24] M. Del Zoppo, C. Castiglioni and G. Zerbi, Nonlinear Optics, vol.9, pp 73, 1995.
[25] C. Adant, M. Dupuis and J.L. Bredas, "Ab initio study of the nonlinear optical properties of urea: Electron correlation and dispersion effects." International Journal of Quantum Chemistry, vol.56, pp 497-507, 1995.