硫代巴比妥酸多晶型的太赫兹光谱和DFT理论分析

doi:10.3964/j.issn.1000-0593(2017)12-3677-06

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Abstract 2-Thiobarbituric acid (TBA) is one of the most polymorphic rich molecular solids currently known. Here, five most common polymorphs of TBA (form Ⅰ, Ⅱ, Ⅲ, Ⅳ and hydrate) were investigated using terahertz time-domain spectroscopy (THz-TDS). All results of the terahertz spectra showed that there were significantly different absorption features for polymorphs, which indicated that THz-TDS technique could effectively identify different types of TBA polymorphs. Form Ⅳ belongs to the tautomeric polymorph, and the absorption features of form Ⅳ at 0.65(broad band), 1.02 and 1.41 THz are significantly different from physical mixture of form Ⅰ and form Ⅱ. Density functional theory (DFT) calculation was performed to optimize two possible molecular structures and simulate the corresponding vibrational spectra. The theoretical result showed that simulated structure (form a) had absorption peaks at 0.41/0.47, 0.89 and 1.35 THz, which agrees with the THz experimental spectrum. Therefore, it is confirmed that, in the TBA form Ⅳ, the first hydrogen bond is formed between thione S7 of isomer A and amide H23 of isomer B in the structure of form Ⅳ, while the second one is constituted by amide H13 of isomer A and thione S20 of isomer B. The characteristic absorption modes of form Ⅳare also assigned based on the simulation results of DFT calculation.

Key words：2-thiobarbituric acid(TBA); Polymorph; Hydrogen bond; Terahertz time-domain spectroscopy (THz-TDS); Density functional theory (DFT)

Received: 2015-06-01 Accepted: 2015-12-30

ZTFLH:

O657.3

Corresponding Authors: DU Yong E-mail: yongdu@cjlu.edu.cn

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http://www.gpxygpfx.com/EN/10.3964/j.issn.1000-0593(2017)12-3677-06 OR http://www.gpxygpfx.com/EN/Y2017/V37/I12/3677

[1] Cornel J, Lindenberg C, Mazzotti M. Crystal Growth & Design, 2009, 9(1): 243.
[2] Byrn S R, Xu W, Newman A W. Advanced Drug Delivery Reviews, 2001, 48(1): 115.
[3] Soto C T, Ramos J M, Costa A C, et al. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2013, 114: 475.
[4] Calas M, Martinez J. Comptes Rendus de l’ Academie des Sciences Serie Ⅲ: Sciences de la Vie, 1967, 265: 631.
[5] Chierotti M R, Ferrero L, Garino N, et al. Chemistry-A European Journal, 2010, 16(14): 4347.
[6] Chierotti M R, Gobetto R, Pellegrino L, et al. Crystal Growth & Design, 2008, 8(5): 1454.
[7] Bakalska R I, Delchev V B. Acta Chimica Slovenica, 2012, 59(1): 75.
[8] Zuccarello F, Buemi G, Gandolfo C, et al. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy, 2003, 59(1): 139.
[9] Tothadi S, Bhogala B R, Gorantla A R, et al. Chemistry-an Asian Journal, 2012, 7(2): 330.
[10] Blake A J, Lin X, Schroder M, et al. Acta Crystallographica. Section C, Crystal Structure Communications, 2004, 60(4): o226.
[11] Desiraju G R. Journal of Chemical Society, Perkin Transactions 2, 1983, 7: 1025.
[12] Bhatt P M, Desiraju G R. Chemical Communications (Cambridge, England), 2007, 20: 2057.
[13] Sharma R P, Singh A, Venugopalan P, et al. Journal of Molecular Structure, 2010, 973(1-3): 27.
[14] XU Jing-zhou, ZHANG Xi-cheng(许景周，张希成). Technology and Applications of Terahertz Wave(太赫兹波科学技术与应用). Beijing: Peking University Press(北京: 北京大学出版社)，2007. 1.
[15] Du Y, Xia Y, Zhang H L, et al. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2013, 111: 192.
[16] King M D, Korter T M. Crystal Growth & Design, 2011, 11(5): 2006.
[17] FANG Hong-xia, ZHANG Qi, ZHANG Hui-li, et al(方虹霞, 张琪, 张慧丽, 等). Acta Physico-Chimica Sinica(物理化学学报), 2015, 31(2): 22.
[18] Hakey P M, Allis D G, Hudson M R, et al. The Journal of Physical Chemistry A, 2010, 114: 4364.
[19] Steiner T, Koellner G. Chemical Communications, 1997, 13: 1207.
[20] Du Y, Zhang H L, Xue J D, et al. Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy, 2015, 139: 488.
[21] WANG Xue-mei, WANG Wei-ning(王雪美, 王卫宁). Acta Chimica Sinica(化学学报), 2008, 66(20): 2248.