Artigos
Estudo conformacional através de simulação computacional, espectroscópico, ONL, HOMO–LUMO e reactividade de 1,3,5-trifenilpirazol
Publicado 2019-01-17
Palavras-chave
- química computacional,
- teoria funcional de densidade (DFT),
- 1,3,5-trifenilpirazol,
- ótica não linear,
- orbitais HOMO-LUMO
- descritores de reatividade ...Mais
Como Citar
Blanco-Acuña, Édgar F., Pérez-Hincapié, L., Pérez-Gamboa, A., Castellar-Ortega, G., & Cely-Bautista, M. (2019). Estudo conformacional através de simulação computacional, espectroscópico, ONL, HOMO–LUMO e reactividade de 1,3,5-trifenilpirazol. REVISTA ION, 31(2). https://doi.org/10.18273/revion.v31n2-2018004
Resumo
Os parâmetros estruturais do 1,3,5-trifenilpirazole foram determinados com DFT/cam-B3LYP com o conjunto de bases 6-311++G(d,p). Os resultados da estrutura molecular otimizada são apresentados e comparados com os dados de raios-X disponíveis da molécula ou moléculas muito semelhantes. Uma análise completa dos espectros observados das medições espectrais de FT-IR, RMN (1H e 13C) e absorção UV-Vis com TD-DFT na mesma função e conjunto de bases é fornecida. As propriedades NLO desta molécula também foram investigadas. As distribuições de cargas NPA e MEP estão correlacionadas. Os resultados calculados e os resultados experimentais são discutidos e correlacionados.
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Referências
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[23] Wazzan N, Al-Qurashi O, Faidallah H. DFT/ and TD-DFT/PCM calculations of molecular structure, spectroscopic characterization, NLO and NBO analyses of 4-(4-chlorophenyl) and 4-[4-(dimethylamino) phenyl]-2-oxo-1,2,5,6-tetrahydrobenzo[H]quinoline-3-carbonitrile dyes. J. Mol. Liq. 2016;223:29-47.
[24] Gil D, Defonsi M, Estévez-Hernández O, Duque J, Reguera E. Quantum chemical studies on molecular structure, spectroscopic (IR, Raman, UV–Vis), NBO and HOMO-LUMO analysis of 1-benzyl-3-(2-furoyl) thiourea, Spectrochim. Acta A. 2015;145:553-62.
[25] Sundaraganesan N, Ilakiamani S, Saleem H, Wojciechowski P, Michalska D. FT-Raman and FT-IR spectra, vibrational assignments and density functional studies of 5-bromo-2-nitropyridine, Spectrochim. Acta A. 2005;61:2995–3001.
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[33] Nakamichi N, Kawashita Y, Hayashi M. Oxidative aromatization of 1,3,5-Trisubstituted pyrazolines and hantzsch 1,4-dihydropyridines by Pd/C in acetic acid. Org. Lett. 2002;4(22):3955-7.
[34] Han B, Liu Z, Liu Q, Yang L, Liu Z-L, Yu W. An efficient aerobic oxidative aromatization of Hantzsch 1,4-dihydropyridines and 1,3,5-trisubstituted pyrazolines. Tetrahedron. 2006;62(11):2492-96.
[35] Carrillo J, Cossı́o, F, Dı́az-Ortiz A, Gómez-Escalonilla M, Begoña A, Moreno A, Prieto P. A complete model for the prediction of 1H- and 13C-NMR chemical shifts and torsional angles in phenyl-substituted pyrazoles”. Tetrahedron. 2001;57:4179-87.
[36] Begtrup M, Vedsù P, Cabildo P, Claramunt RM, Elguero J, Meutermans W. 13C NMR of pyrazoles. Magn. Reson. Chem. 1992;30:107-68.
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[38] Arjunan V, Balamourougane P, Kalaivani M, Raj A, Mohan S. Experimental and theoretical quantum chemical investigations of 8-hydroxy-5-nitroquinoline. Spectrochim. Acta A. 2012;96:506-16.
[39] Fukui K. Role of frontier orbitals in chemical reactions. Science. 1982;218:747-54.
[40] López J, Ensuncho A, Robles J. Estudio teórico de la reactividad química y biológica de cisplatino y algunos derivados con actividad anticancerosa. Información Tecnológica. 2013;24(3):3-14.
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[43] Chandrasekaran K, Kumar R. Structural, spectral, thermodynamical, NLO, HOMO, LUMO and NBO analysis of fluconazole. Spectrochim. Acta A. 2015;150:974-91.
[2] Morse G, Gantz J, Steirer K, Armstrong N, Bender T. Pentafluorophenoxy Boron Subphthalocyanine (F5BsubPc) as a Multifunctional Material for Organic Photovoltaics. Appl. Mater. Interfaces. 2014;6:1515-24.
[3] Ronchi M, Pizzotti M, Orbelli A, Righetto S, Ugo R, Mussini P, et al. Second-order nonlinear optical (NLO) properties of a multichromophoric system based on an ensemble of four organic NLO chromophores nanoorganized on a cyclotetrasiloxane architecture. J. Phys. Chem. C. 2009; 113: 2745-60.
[4] Andreu R, Garín J, Orduna J, Alcalá R, Villacampa B. Novel NLO-phores with proaromatic donor and acceptor groups. Org. Lett. 2003;5:3143-46.
[5] Ruiz M, Casado J, Hernández V, López J, Orduna J, Villacampa B, et al. Electronic, optical, and vibrational properties of bridged dithienylethylene-based NLO chromophores. J. Phys. Chem. C. 2008;112: 3109-20.
[6] Saravanan S, Balachandran V. Conformational stability, spectroscopic (FT-IR, FT-Raman and UV–Vis) analysis, NLO, NBO, FMO and Fukui function analysis of 4-hexylacetophenone by density functional theory. Spectrochim. Acta A. 2015;138:406-23.
[7] Demircioglu Z, Albayrak C, Büyükgüngör O. The spectroscopic (FT-IR, UV-vis), Fukui function, NLO, NBO, NPA and tautomerism effect analysis of (E)-2-[(2-hydroxy-6-methoxybenzylidene)amino]benzonitrile. Spectrochim. Acta A. 2015;139:539-48.
[8] Gondek E. Photovoltaic solar cells based on pyrazole derivative. Mater. Lett. 2013;112:94-6.
[9] Amudha S, Austin S, Suthanthiraraj R, Maruthamuthu P. Performance characteristics of pyrazole as an effective dopant in a blended polymer electrolyte for nanocrystalline dye-sensitized solar cell applications. Chem. Sci. Trans. 2013;2:S141-S146.
[10] Ocaya R, Al-Sehemi G.A., Al-Ghamdi A, El-Tantawy F, Yakuphanoglu F. “Organic semiconductor photosensors”. Journal of Alloys and Compounds, 2017;702:520-30.
[11] Costa J, Taveira R, Lima C, Mendes A, Santos L. Optical band gaps of organic semiconductor materials. Optical Materials, 2016;58:51-60.
[12] Akhtari K, Hassanzadeh K, Fakhraei B, Fakhraei N, Hassanzadeh H, Zarei A. A density functional theory study of the reactivity descriptors and antioxidant behavior of Crocin. Comput. Theor. Chem. 2013;1013:123-29.
[13] Tathe A, Gupta V, Sekar N. Synthesis and combined experimental and computational investigations on spectroscopic and photophysical properties of red emitting 3-styryl coumarins. Dyes and Pigments. 2015;119:49-55.
[14] Suvitha A, Periandy S, Gayathri P. Vibrational frequency analysis, FT-IR, FT-Raman, ab initio, HF and DFT studies, NBO, HOMO-LUMO and electronic structure calculations on pycolinaldehyde oxime. Spectrochimica Acta A. 2014;117:216-24.
[15] Romani E, Brandán S. Structural and spectroscopic studies of two 1,3-benzothiazole tautomers with potential antimicrobial activity in different media. Prediction of their reactivities. Computational andTheoretical Chemistry, 2015;1061:89-99.
[16] Romani E, Ladetto M, Brandán S. Structural and vibrational studies of the potential anticancer agent, 5-difluoromethyl-1,3,4-thiadiazole-2-amino by DFT calculations. Comput. Theor. Chem. 2013;1011:57-64.
[17] Kutsyna L, Korneeva O. The electronic structure of 1,3,5-triphenylpyrazole. J. App. Spec, 1971;15(2):1027-31.
[18] Akhtari K, Hassanzadeh K, Fakhraei B, Fakhraei N, Hassanzadeh H, Zarei S. A density functional theory study of the reactivity descriptors and antioxidant behavior of Crocin. Comput. Theor. Chem. 2013;1013:123-29.
[19] Nuñez F, Arguello E, Vivas R. Density functional study on electronic structures and reactivity in methyl-substituted chelates used in organic light-emitting diodes. Int. J. Quantum Chem, 2010;110(9):1622-36.
[20] Dennington R, Keith T, Millam J. GaussView, Version 5. Semichem Inc., Shawnee Mission, KS, (2009).
[21] Frisch M, Trucks G, Schlegel H, Scuseria G, Robb M, Cheeseman J, et. al. Gaussian 09, Revision A.02, Gaussian, Inc., Wallingford CT, 2009.
[22] Paschoal D, Dos Santos H. Assessing the quantum mechanical level of theory for prediction of linear and nonlinear optical properties of push-pull organic molecules. J. Mol. Mod. 2013;19:2079-90.
[23] Wazzan N, Al-Qurashi O, Faidallah H. DFT/ and TD-DFT/PCM calculations of molecular structure, spectroscopic characterization, NLO and NBO analyses of 4-(4-chlorophenyl) and 4-[4-(dimethylamino) phenyl]-2-oxo-1,2,5,6-tetrahydrobenzo[H]quinoline-3-carbonitrile dyes. J. Mol. Liq. 2016;223:29-47.
[24] Gil D, Defonsi M, Estévez-Hernández O, Duque J, Reguera E. Quantum chemical studies on molecular structure, spectroscopic (IR, Raman, UV–Vis), NBO and HOMO-LUMO analysis of 1-benzyl-3-(2-furoyl) thiourea, Spectrochim. Acta A. 2015;145:553-62.
[25] Sundaraganesan N, Ilakiamani S, Saleem H, Wojciechowski P, Michalska D. FT-Raman and FT-IR spectra, vibrational assignments and density functional studies of 5-bromo-2-nitropyridine, Spectrochim. Acta A. 2005;61:2995–3001.
[26] CambridgeSoft. PerkinElmer. Versión 13.0.0.3015. 1996-2012.
[27] Mestrelab Research S.L. Version 60.2.-5475. 2009.
[28] Trotter J. Bond lengths in benzene derivatives: Hybridization or resonance. Tetrahedron. 1960;8:13-22.
[29] Shetty M, Samant S. Sulfamic Acid (H2NSO3H): A low-cost, mild, and efficient catalyst for the synthesis of substituted N-Phenylpyrazoles under solvent-free conditions. Synthetic Commun. 2012;42:1411-18.
[30] Sharma Y. Elementary Organic Spectroscopy, principles and chemical applications. India: Chande & Company Ltd.; 1994.
[31] Krishnakumar V, Manohar S, Nagalakshmi R. Crystal growth and characterization of N-hydroxyphthalimide (C8H5NO3) crystal. Spectrochim. Acta A. 2008;71:110-5.
[32] Ananthnag G, Adhikari A, Balakrishna M. Iron-catalyzed aerobic oxidative aromatization of 1,3,5-trisubstituted pyrazolines. Catal. Commun. 2014;43:240-3.
[33] Nakamichi N, Kawashita Y, Hayashi M. Oxidative aromatization of 1,3,5-Trisubstituted pyrazolines and hantzsch 1,4-dihydropyridines by Pd/C in acetic acid. Org. Lett. 2002;4(22):3955-7.
[34] Han B, Liu Z, Liu Q, Yang L, Liu Z-L, Yu W. An efficient aerobic oxidative aromatization of Hantzsch 1,4-dihydropyridines and 1,3,5-trisubstituted pyrazolines. Tetrahedron. 2006;62(11):2492-96.
[35] Carrillo J, Cossı́o, F, Dı́az-Ortiz A, Gómez-Escalonilla M, Begoña A, Moreno A, Prieto P. A complete model for the prediction of 1H- and 13C-NMR chemical shifts and torsional angles in phenyl-substituted pyrazoles”. Tetrahedron. 2001;57:4179-87.
[36] Begtrup M, Vedsù P, Cabildo P, Claramunt RM, Elguero J, Meutermans W. 13C NMR of pyrazoles. Magn. Reson. Chem. 1992;30:107-68.
[37] Ando W, Sato R, Yamashita M, Akasaka T, Miyazaki H. Quenching of singlet oxygen by 1,3,5-triaryl-2-pyrazolines. J. Org. Chem. 1983;48:542-6.
[38] Arjunan V, Balamourougane P, Kalaivani M, Raj A, Mohan S. Experimental and theoretical quantum chemical investigations of 8-hydroxy-5-nitroquinoline. Spectrochim. Acta A. 2012;96:506-16.
[39] Fukui K. Role of frontier orbitals in chemical reactions. Science. 1982;218:747-54.
[40] López J, Ensuncho A, Robles J. Estudio teórico de la reactividad química y biológica de cisplatino y algunos derivados con actividad anticancerosa. Información Tecnológica. 2013;24(3):3-14.
[41] Pearson R. Hard and soft acids and Basis. J. Am. Chem. Soc. 1963;85(22):3533-39.
[42] Parr R, Pearson R. Absolute hardness: companion parameter to absolute electronegativity. J.Am. Chem. Soc. 1983;105(26):7512-16.
[43] Chandrasekaran K, Kumar R. Structural, spectral, thermodynamical, NLO, HOMO, LUMO and NBO analysis of fluconazole. Spectrochim. Acta A. 2015;150:974-91.