取代基对1-甲基尿嘧啶与N-甲基乙酰胺氢键复合物中氢键强度的影响

doi:10.3866/PKU.WHXB201209263

物理化学学报 >> 2012, Vol. 28 >> Issue (12): 2809-2816.doi: 10.3866/PKU.WHXB201209263

取代基对1-甲基尿嘧啶与N-甲基乙酰胺氢键复合物中氢键强度的影响

刘冬佳, 王长生

辽宁师范大学化学化工学院, 辽宁大连 116029

收稿日期:2012-07-27 修回日期:2012-09-25 发布日期:2012-11-14
通讯作者: 王长生 E-mail:chwangcs@lnnu.edu.cn
基金资助:
国家自然科学基金(20973088, 21173109,21133005)和教育部高等学校博士点基金(20102136110001)资助项目

Effect of Substituents on Hydrogen Bond Strength in Hydrogen-Bonded N-methylacetamide and Uracil Complexes

LIU Dong-Jia, WANG Chang-Sheng

School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China

Received:2012-07-27 Revised:2012-09-25 Published:2012-11-14
Supported by:
The project was supported by the National Natural Science Foundation of China (20973088, 21173109, 21133005) and the Specialized Research Fund for the Doctoral Program of Higher Education of China (20102136110001).

摘要/Abstract

摘要：

使用密度泛函理论B3LYP方法和二阶微扰理论MP2方法对由1-甲基尿嘧啶与N-甲基乙酰胺所形成的氢键复合物中的氢键强度进行了理论研究, 探讨了不同取代基取代氢键受体分子1-甲基尿嘧啶中的氢原子对氢键强度的影响和氢键的协同性. 研究表明: 供电子取代基使N－H…O＝C氢键键长r(H…O)缩短, 氢键强度增强; 吸电子取代基使N－H…O＝C氢键键长r(H…O)伸长, 氢键强度减弱. 自然键轨道(NBO)分析表明: 供电子基团使参与形成氢键的氢原子的正电荷增加, 使氧原子的负电荷增加, 使质子供体和受体分子间的电荷转移量增多; 吸电子基团则相反. 供电子基团使N－H…O＝C氢键中氧原子的孤对电子轨道n(O)对N－H的反键轨道σ^*(N－H)的二阶相互作用稳定化能增强, 吸电子基团使这种二阶相互作用稳定化能减弱. 取代基对与其相近的N－H…O＝C氢键影响更大.

关键词: 氢键复合物, 取代基, 氢键强度, 自然键轨道分析, 氢键协同性

Abstract:

Theoretical calculations on a series of N－H…O＝C hydrogen-bonded complexes containing 1-methyluracil and N-methylacetamide were carried out using B3LYP and MP2 methods. Substituent effects in the hydrogen bond acceptor molecule (1-methyluracil) on the hydrogen bond strength and hydrogen bond cooperativity were explored. The calculation results show that electron donating groups shorten the H…O distance and strengthen the N－H…O＝C hydrogen bond, whereas electron withdrawing groups lengthen the H…O distance and weaken the N－H…O＝C hydrogen bond. Natural bond orbital (NBO) analysis further indicates that electron donating groups result in a larger positive charge on the H atom and a larger negative charge on the O atom in the N－H…O＝C bond, and result in increased charge transfer between the proton donor and acceptor molecules. Electron withdrawing groups show the opposite results. NBO analysis also indicates that electron donating groups result in larger second-order interaction energies between the oxygen lone pair and the N － H antibonding orbital when compared to the 1-methyluracil-containing complex (R=H), while electron withdrawing groups result in smaller second-order interaction energies.

Key words: Hydrogen-bonded complex, Substituent, Hydrogen bond strength, Natural bond orbital analysis, Hydrogen bond cooperativity

点击下载补充材料PDF格式文件

刘冬佳, 王长生. 取代基对1-甲基尿嘧啶与N-甲基乙酰胺氢键复合物中氢键强度的影响[J]. 物理化学学报, 2012, 28(12), 2809-2816. doi: 10.3866/PKU.WHXB201209263

LIU Dong-Jia, WANG Chang-Sheng. Effect of Substituents on Hydrogen Bond Strength in Hydrogen-Bonded N-methylacetamide and Uracil Complexes[J]. Acta Phys. -Chim. Sin. 2012, 28(12), 2809-2816. doi: 10.3866/PKU.WHXB201209263

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201209263

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I12/2809

参考文献

(1) Desiraju, G. R.; Steiner, T. The Weak of Hydrogen Bond;Oxford University Press: New Nork, 1999; pp 343-412.
(2) Jeffrey, G. A. An Introduction to Hydrogen Bonding; OxfordUniversity Press: New York, 1997; pp 184-212.
(3) Scheiner, S. Hydrogen Bonding: A Theoretical Perspective;Oxford University Press: New York, 1997; pp 105-117.
(4) Chalaris, M.; Samios, J. J. Phys. Chem. B 1999, 103, 1161.doi: 10.1021/jp982559f
(5) Mohajeri, A.; Nobandegani, F. F. J. Phys. Chem. A 2008, 112,281. doi: 10.1021/jp075992a
(6) Sun, C. L.;Wang, C. S. Sci. China Ser. B-Chem. 2009, 39 (6),481. [孙长亮, 王长生. 中国科学B 辑: 化学, 2009, 39 (6),481.]
(7) Jiang, X. N.;Wang, C. S. ChemPhysChem 2009, 10, 3330.doi: 10.1002/cphc.200900591
(8) Li, Y.; Jiang, X. N.;Wang, C. S. J. Comput. Chem. 2011, 32,953. doi: 10.1002/jcc.v32.5
(9) Kolew, S. K.; Petkow, P. S.; Rangelow, M. A.; Vayssilow, G. N.J. Phys. Chem. A 2011, 115, 14054. doi: 10.1021/jp204313f
(10) Angelina, E. L.; Peruchena, N. M. J. Phys. Chem. A 2011, 115,4701. doi: 10.1021/jp1105168
(11) Ji, C. G.; Zhang, Z. H. J. Phys. Chem. B 2011, 115, 12230. doi: 10.1021/jp205907h
(12) Izgorodina, E. I.; MacFarlane, D. R. J. Phys. Chem. B 2011,115, 14659. doi: 10.1021/jp208150b
(13) Dong, H.; Hua,W. J.; Li, S. H. J. Phys. Chem. A 2007, 111,2941.
(14) Vargas, R.; Garza, J.; Friesner, R. A.; Stern, H.; Hay, B. P.;Dixon, D. A. J. Phys. Chem. A 2001, 105, 4963. doi: 10.1021/jp003888m
(15) Kawahara, S.; Kobori, A.; Sekine, M.; Taira, K.; Uchimaru, T.J. Phys. Chem. A 2001, 105, 10596. doi: 10.1021/jp0124645
(16) Kawahara, S.; Uchimaru, T.; Taira, K.; Sekine, M. J. Phys. Chem. A 2001, 105, 3894.
(17) Sun, C. L.; Zhang, Y.; Jiang, X. N.;Wang, C. S.; Yang, Z. Z. Sci. China Ser. B-Chem. 2008, 38 (9), 762. [孙长亮, 张艳, 姜笑楠, 王长生, 杨忠志. 中国科学B 辑: 化学, 2008, 38 (9), 762.]
(18) Sun, C. L.; Jiang, X. N.;Wang, C. S. J. Comput. Chem. 2009,30, 2567. doi: 10.1002/jcc.v30:15
(19) Wang, C. S.; Zhang, Y.; Gao, K.; Yang, Z. Z. J. Chem. Phys.2005, 123, 024307. doi: 10.1063/1.1979471
(20) Zhang, Y.;Wang, C. S. J. Comput. Chem. 2009, 30, 1251. doi: 10.1002/jcc.v30:8
(21) Sun, C. L.;Wang, C. S. J. Mol. Struct. -Theochem 2010, 956, 38.doi: 10.1016/j.theochem.2010.06.020
(22) Jiang, X. N.; Sun, C. L.;Wang, C. S. J. Comput. Chem. 2010,31, 1410.
(23) Chen, Y. F.; Dannenberg, J. J. J. Am. Chem. Soc. 2006, 128,8100. doi: 10.1021/ja060494l
(24) Nobko, N.; Dannenberg, J. J. J. Phys. Chem. A 2003, 107, 6688.doi: 10.1021/jp0345497
(25) Nobko, N.; Dannenberg, J. J. J. Phys. Chem. A 2003, 107,10389.
(26) Zhao, Y. L.;Wu, Y. D. J. Am. Chem. Soc. 2002, 124, 1570. doi: 10.1021/ja016230a
(27) Wu, Y. D.; Zhao, Y. L. J. Am. Chem. Soc. 2001, 123, 5313. doi: 10.1021/ja003482n
(28) Tan, H.W.; Qu,W.W.; Chen, G. J.; Liu, R. Z. J. Phys. Chem. A2005, 109, 6303. doi: 10.1021/jp051444q
(29) Hunter, K. C.; Millen, A. L.;Wetmore, S. D. J. Phys. Chem. B2007, 111, 1858. doi: 10.1021/jp066902p
(30) Jeong, E.; Kim, H.; Lee, S.W.; Han, K. Mol. Cells 2003, 16,161.
(31) Cheng, A. C.; Frankel, A. D. J. Am. Chem. Soc. 2004, 126, 434.doi: 10.1021/ja037264g
(32) Tkachenko, M. Y.; Boryskina, O. P.; Shestopalova, A. V.;Tolstorukov, M. Y. Int. J. Quantum Chem. 2010, 110, 230. doi: 10.1002/qua.v110:1
(33) Frish, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gassian 03,Revision D.01; Gaussian Inc.: Pittsburgh, PA, 2003.

[1]	雷永久, 王旭, 王治业, 周疆豪, 陈海舰, 梁蕾, 李云川, 肖博怀, 常帅. 噻吩锚定基团的结构修饰对分子-电极结合的影响[J]. 物理化学学报, 2023, 39(11): 2212023 - .
[2]	何亚鹏,陈荣玲,王超男,李红东,黄卫民,林海波. 掺硼金刚石电极电催化氧化酚类有机物的取代基效应[J]. 物理化学学报, 2017, 33(11): 2253 -2260 .
[3]	陈华彬,章小慧,龚丽珍,何婧,许旋,徐志广,刘海洋. β位取代基对咔咯锰(Ⅴ)氧配合物电子吸收光谱的影响[J]. 物理化学学报, 2016, 32(8): 1983 -1989 .
[4]	罗青青,曹朝暾,曹晨忠. 取代基效应对二取代二苯基硝酮还原电位的影响[J]. 物理化学学报, 2016, 32(7): 1691 -1698 .
[5]	刘玉震, 黎安勇. H₂XP…SHY复合物中磷键与硫键的理论研究[J]. 物理化学学报, 2015, 31(3): 435 -440 .
[6]	曹朝暾, 魏佰影, 曹晨忠. 取代基效应对N-4-取代苯亚甲基苯胺与N-4-取代苯亚甲基环己胺NMR和UV光谱影响的差异性[J]. 物理化学学报, 2015, 31(2): 204 -210 .
[7]	许泽清, 高保娇, 侯晓东. 芳环上硝基取代基对苯甲酸功能化聚苯乙烯-Eu（Ⅲ）配合物光致发光性能的双重影响[J]. 物理化学学报, 2014, 30(4): 745 -752 .
[8]	王长生, 刘朋, 于楠. 槲皮素与尿嘧啶和胸腺嘧啶氢键的结合位点[J]. 物理化学学报, 2013, 29(06): 1173 -1182 .
[9]	曹晨忠, 武亚新. 用扩展的Istomin-Palm模型估算双向延伸化合物R1-Y-R2生成焓[J]. 物理化学学报, 2013, 29(01): 35 -42 .
[10]	赵东波, 荣春英, 苏曼, 苏文, 尹笃林, 刘述斌. 顺式效应的起源: 双取代乙烯衍生物的密度泛函理论研究[J]. 物理化学学报, 2013, 29(01): 43 -54 .
[11]	马华璇, 郑燕玲, 詹益仕, 谭莹, 黄晓, 彭琦, 许旋. 金属串配合物[Cr₃(dpa)₄LL'](dpa=dipyridylamide; L, L'=Cl, BF₄, CCPh)的Cr—Cr成键特性[J]. 物理化学学报, 2012, 28(07): 1637 -1644 .
[12]	赵高峰, 王银亮, 孙建敏, 王渊旭. Au₁₂M (M=Na, Mg, Al, Si, P, S, Cl)团簇的结构、稳定性和电子性质[J]. 物理化学学报, 2012, 28(06): 1355 -1360 .
[13]	张愚, 马宁, 王伟周. 氢键复合物中键长变化与振动频率移动相关性重访[J]. 物理化学学报, 2012, 28(03): 499 -503 .
[14]	郑文锐, 徐菁利, 熊瑞. N—O键解离焓的密度泛函理论研究[J]. 物理化学学报, 2010, 26(09): 2535 -2542 .
[15]	张敏, 郑艳萍, 姜笑楠, 王长生. 取代基对N—H…O=C氢键三聚体中氢键强度的影响[J]. 物理化学学报, 2010, 26(03): 735 -739 .

取代基对1-甲基尿嘧啶与N-甲基乙酰胺氢键复合物中氢键强度的影响

Effect of Substituents on Hydrogen Bond Strength in Hydrogen-Bonded N-methylacetamide and Uracil Complexes

PDF

赞

可视化

摘要/Abstract

支持信息

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0