Citation: Xiao Xuezhu, Cao Xiaofang, Zhao Dongbo, Rong Chunying, Liu Shubin. Quantification of Molecular Basicity for Amines: a Combined Conceptual Density Functional Theory and Information-Theoretic Approach Study[J]. Acta Physico-Chimica Sinica, ;2020, 36(11): 190603. doi: 10.3866/PKU.WHXB201906034 shu

Quantification of Molecular Basicity for Amines: a Combined Conceptual Density Functional Theory and Information-Theoretic Approach Study

1.
College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. China
2.
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China
3.
Research Computing Center, University of North Carolina, Chapel Hill, NC 27599-3420, USA

Corresponding author: Rong Chunying, rongchunying@aliyun.com Liu Shubin, shubin@email.unc.edu
Received Date: 6 June 2019
Revised Date: 1 July 2019
Accepted Date: 12 July 2019
Available Online: 17 July 2019
Fund Project: the Hunan Provincial Natural Science Foundation of China 2017JJ3201the National Natural Science Foundation of China 21503076The project was supported by the National Natural Science Foundation of China (21503076) and the Hunan Provincial Natural Science Foundation of China (2017JJ3201)

The pair of molecular acidity and basicity is one of the most widely used chemical concepts in chemistry, biology, and other related fields. Nevertheless, quantitative determination of these intrinsic physical properties from the perspective of theory and computation is still an unresolved task at present. Earlier, we proposed to utilize the molecular electrostatic potential and natural atomic orbital from conceptual density functional theory for this purpose. Later, we also proposed utilizing quantities from the information-theoretic approach in the density functional reactivity theory such as Shannon entropy, Fisher information, and information gain to quantify electrophilicity, nucleophilicity, regioselectivity, and stereoselectivity. The latter was successfully applied later to five series of molecular systems for determining the molecular acidity, including singly and doubly substituted benzoic acids, benzenesulfonic acids, benzeneseleninic acids, phenols, and alkyl carboxylic acids, whose validity and effectiveness have been sufficiently corroborated. As a continuation of our recent efforts along this line, in this work, we generalize our previous approaches by combining these two approaches together as a new set of descriptors to quantify the molecular basicity. The applicability and usefulness of our new approach are demonstrated hereby by three types of amines, namely, primary, secondary, and tertiary amines, with a total of 179 systems. We show that this new set of descriptors, including the molecular electrostatic potential or its equivalence, the natural valence atomic orbital energy, and quantities from information-theoretic approach such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy, information gain, Onicescu information energy, and relative Rényi entropy, is able to accurately predict the experimental pK_a values for the three types of amines. Our findings confirm that each of these quantities possesses strong linear correlation with the experimental pK_a value, though less significantly than expected. Moreover, when combined, these quantities can yield accurate and quantitative models for determining the molecular basicity of all the three types of amines. The reason behind this is that all these descriptors are simple electron density functionals. According to the basic theorem of density functional theory, they should contain adequate information for the determination of all the physio-chemical properties in the ground state of molecular systems, including molecular acidity and basicity. Our present results predict that this new approach should be readily applicable to many other molecular species, thereby providing an effective and robust approach to appreciate chemical concepts such as acidity and basicity.
- pK_a,
- Amine,
- Conceptual density functional theory,
- Information-theory approach
1. [1]
  Lowry, T. M. J. Chem. Technol. Biotechnol. 1923, 42, 43. doi: 10.1002/jctb.5000420302 doi: 10.1002/jctb.5000420302
2. [2]
  Lowry, T. M. J. Chem. Technol. Biotechnol. 1923, 42, 1048. doi: 10.1002/jctb.5000424402 doi: 10.1002/jctb.5000424402
3. [3]
  Bronsted, J. N. J. Chem. Phys. 1925, 30, 777. doi: 10.1021/j150264a007 doi: 10.1021/j150264a007
4. [4]
  Everett, D. H.; Wynne-Jones, W. F. K. Trans. Faraday Soc. 1939, 35, 1380. doi: 10.1039/TF9393501380 doi: 10.1039/TF9393501380
5. [5]
  Lias, S. G.; Liebman, J. F.; Levin, R. D. J. Phys. Chem. Ref. Data 1984, 13, 695. doi: 10.1063/1.555719 doi: 10.1063/1.555719
6. [6]
  Raczyńska, E. D.; Gal, J. F.; Maria, P. C. Chem. Rev. 2016, 116, 13454. doi: 10.1021/acs.chemrev.6b00224 doi: 10.1021/acs.chemrev.6b00224
7. [7]
  Pliego, J. R. Chem. Phys. Lett. 2003, 367, 145. doi: 10.1016/S0009-2614(02)01686-X doi: 10.1016/S0009-2614(02)01686-X
8. [8]
  Casasnovas, R.; Ortega-Castro, J.; Frau, J.; Donoso, J.; Muñoz, F. Int. J. Quantum Chem. 2014, 114, 1350. doi: 10.1002/qua.24699 doi: 10.1002/qua.24699
9. [9]
  Hernandez, C. J. Chil. Chem. Soc. 2016, 61, 3160. doi: 10.4067/S0717-97072016000400002 doi: 10.4067/S0717-97072016000400002
10. [10]
  Geerlings, P.; De Proft, F.; Langenaeker, W. Chem. Rev. 2003, 103, 1793. doi: 10.1021/cr990029p doi: 10.1021/cr990029p
11. [11]
  Liu, S. B. Acta Phys. -Chim. Sin. 2009, 25, 590. doi: 10.3866/PKU.WHXB20090332
12. [12]
  Parr, R. G.; Yang, W. T. Density Functional Theory of Atoms and Molecules; Oxford University Press: New York, USA, 1989.
13. [13]
  Liu, S. B.; Schauer, C. K.; Pedersen, L. G. J. Chem. Phys. 2009, 131, 164107. doi: 10.1063/1.3251124 doi: 10.1063/1.3251124
14. [14]
  Liu, S. B.; Pedersen, L. G. J. Phys. Chem. A 2009, 113, 3648. doi: 10.1021/jp811250r doi: 10.1021/jp811250r
15. [15]
  Liu, S. B. J. Chem. Phys. 2014, 141, 194109. doi: 10.1063/1.4901898
16. [16]
  Liu, S. B.; Rong, C. Y.; Lu, T. J. Phys. Chem. A 2014, 118, 3698. doi: 10.1021/jp5032702 doi: 10.1021/jp5032702
17. [17]
  Liu, S. B. Acta Phys. -Chim. Sin. 2016, 32, 98. doi: 10.3866/PKU.WHXB201510302
18. [18]
  Liu, S. B.; Rong, C. Y.; Lu, T. Phys. Chem. Chem. Phys. 2017, 19, 1496. doi: 10.1039/C6CP06376D doi: 10.1039/C6CP06376D
19. [19]
  Liu, S. B. J. Chem. Phys. 2007, 126, 191107. doi: 10.1063/1.2741244 doi: 10.1063/1.2741244
20. [20]
  Ali, S. T.; Karamat, S.; Kóňa, J.; Fabian, W. M. F. J. Phys. Chem. A 2010, 114, 12470. doi: 10.1021/jp102266v doi: 10.1021/jp102266v
21. [21]
  Cao, X. F.; Rong, C. Y.; Zhong, A. G.; Lu, T.; Liu, S. B. J. Comput. Chem. 2017, 39, 117. doi: 10.1002/jcc.25090 doi: 10.1002/jcc.25090
22. [22]
  Seiler, N.; Demisch, L.; Schneider, H. Angew. Chem. Int. Ed. 1971, 10, 51. doi: 10.1002/anie.197100511 doi: 10.1002/anie.197100511
23. [23]
  Medina, M. Á.; Urdiales, J. L.; Rodríguez-Caso, C.; Ramírez, F. J.; Sánchez-Jiménez, F. Crit. Rev. Biochem. Mol. Biol. 2003, 38, 23. doi: 10.1080/713609209 doi: 10.1080/713609209
24. [24]
  Huang, Y.; Liu, L.; Liu, W.; Liu, S.; Liu, S. B. J. Phys. Chem. A 2011, 115, 14697. doi: 10.1021/jp209540p doi: 10.1021/jp209540p
25. [25]
  Huang, Y.; Liu, L.; Liu, S. B. Chem. Phys. Lett. 2012, 527, 73. doi: 10.1016/j.cplett.2012.01.014 doi: 10.1016/j.cplett.2012.01.014
26. [26]
  Zhao, D. B.; Rong, C. Y.; Yin, D. L.; Liu, S. B. J. Theor. Comput. Chem. 2013, 12, 1350034. doi: 10.1142/S021963361350034X doi: 10.1142/S021963361350034X
27. [27]
  Liu, S. B. J. Phys. Chem. A 2015, 119, 3107. doi: 10.1021/acs.jpca.5b00443 doi: 10.1021/acs.jpca.5b00443
28. [28]
  Liu, S. B. J. Chem. Phys. 2007, 126, 244103. doi: 10.1063/1.2747247 doi: 10.1063/1.2747247
29. [29]
  Shannon, C. E. J. Bell Syst. Tech. 1948, 27, 379. doi: 10.1002/j.1538-7305.1948.tb01338.x doi: 10.1002/j.1538-7305.1948.tb01338.x
30. [30]
  Stephen, B.; Sears Robert, G.; Dinur, P. U. Isr. J. Chem. 1980, 19, 165. doi: 10.1002/ijch.198000018 doi: 10.1002/ijch.198000018
31. [31]
  Sears, S. B.; Gadre, S. R. J. Chem. Phys. 1981, 75, 4626. doi: 10.1063/1.442578 doi: 10.1063/1.442578
32. [32]
  Fisher, R. A. Math. Proc. Camb. Phil. 1925, 22, 700. doi: 10.1017/S0305004100009580 doi: 10.1017/S0305004100009580
33. [33]
  Rong, C. Y.; Lu, T.; Chattaraj, P. K.; Liu, S. B. Indian J. Chem. A 2014, 53A, 970.
34. [34]
  Ghosh, S. K.; Berkowitz, M.; Parr, R. G. Proc. Natl. Acad. Sci. USA 1984, 81, 8028. doi: 10.1073/pnas.81.24.8028 doi: 10.1073/pnas.81.24.8028
35. [35]
  Nalewajski, R. F.; Parr, R. G. Proc. Natl. Acad. Sci. USA 2000, 97, 8879. doi: 10.1073/pnas.97.16.8879 doi: 10.1073/pnas.97.16.8879
36. [36]
  Nalewajski, R. F.; Parr, R. G. J. Phys. Chem. A 2001, 105, 7391. doi: 10.1021/jp004414q doi: 10.1021/jp004414q
37. [37]
  Parr, R. G.; Ayers, P. W.; Nalewajski, R. F. J. Phys. Chem. A 2005, 109, 3957. doi: 10.1021/jp0404596 doi: 10.1021/jp0404596
38. [38]
  Ayers, P. W. Theor. Chem. Acc. 2006, 115, 370. doi: 10.1007/s00214-006-0121-5 doi: 10.1007/s00214-006-0121-5
39. [39]
  Rong, C. Y.; Lu, T.; Liu, S. B. J. Chem. Phys. 2014, 140, 024109. doi: 10.1063/1.4860969 doi: 10.1063/1.4860969
40. [40]
  Nagy, Á.; Romera, E. Europhys. Lett. 2015, 109, 60002. doi: 10.1209/0295-5075/109/60002 doi: 10.1209/0295-5075/109/60002
41. [41]
  Liu, S. B.; Rong, C. Y.; Wu, Z. M.; Lu, T. Acta Phys. -Chim. Sin. 2015, 31, 2057. doi: 10.3866/PKU.WHXB201509183
42. [42]
  Nagy, Á.; Romera, E. Europhys. Lett. 2015, 109, 60002. doi: 10.1209/0295-5075/109/60002 doi: 10.1209/0295-5075/109/60002
43. [43]
  Tsallis, C. J. Statis. Phys. 1988, 52, 479. doi: 10.1007/BF01016429 doi: 10.1007/BF01016429
44. [44]
  Onicescu, O. C. R. Acad. Sci., Paris, Serie A 1966, 263, 841.
45. [45]
  Hall, H. K. J. Am. Chem. Soc. 1957, 79, 5441. doi: 10.1021/ja01577a030 doi: 10.1021/ja01577a030
46. [46]
  Soloway, S.; Lipschitz, A. J. Org. Chem. 1958, 23, 613. doi: 10.1021/jo01098a603 doi: 10.1021/jo01098a603
47. [47]
  Stevenson, G. W.; Williamson, D. J. Am. Chem. Soc. 1958, 80, 5943. doi: 10.1021/ja01555a014 doi: 10.1021/ja01555a014
48. [48]
  Bissell, E. R.; Finger, M. J. Org. Chem. 1959, 24, 1256. doi: 10.1021/jo01091a024 doi: 10.1021/jo01091a024
49. [49]
  Tuckerman, M. M.; Mayer, J. R.; Nachod, F. C. J. Am. Chem. Soc. 1959, 81, 92. doi: 10.1021/ja01510a020 doi: 10.1021/ja01510a020
50. [50]
  Bryson, A. J. Am. Chem. Soc. 1960, 82, 4871. doi: 10.1021/ja01503a030 doi: 10.1021/ja01503a030
51. [51]
  Bell, R. P. Proton. Chem. 1973, 86. doi: 10.1007/978-1-4757-1592-7_6 doi: 10.1007/978-1-4757-1592-7_6
52. [52]
  Bordwell, F. G.; Algrim, D.; Vanier, N. R. J. Org. Chem. 1977, 42, 1817. doi: 10.1021/jo00430a039 doi: 10.1021/jo00430a039
53. [53]
  Lide, D. R. Handbook of Chemistry and Physics, 88th Ed.; CRC Press: Boca Raton, FL, London, UK, 2007.
54. [54]
  Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724. doi: 10.1063/1.1674902 doi: 10.1063/1.1674902
55. [55]
  Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785 doi: 10.1103/PhysRevB.37.785
56. [56]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913 doi: 10.1063/1.464913
57. [57]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; robb, M. A.; Scalmani, J. R.; Cheeseman, G.; Barone, V.; Mennucci, B.; Peterson, G. A.; et al. Gaussian 09, Revision D.01; Gaussian Inc.: Wallingford, CT, USA. 2009.
58. [58]
  Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.22885 doi: 10.1002/jcc.22885
59. [59]
  Hirshfeld, F. L. Theo. Chim. Acta 1977, 44, 129. doi: 10.1007/BF00549096 doi: 10.1007/BF00549096
60. [60]
  Rong, C. Y.; Lu, T.; Ayers, P. W.; Chattaraj, P. K.; Liu, S. B. Phys. Chem. Chem. Phys. 2015, 17, 4977. doi: 10.1039/C4CP05609D doi: 10.1039/C4CP05609D
61. [61]
  Becke, A. D. J. Chem. Phys. 1988, 88, 2547. doi: 10.1063/1.454033 doi: 10.1063/1.454033
62. [62]
  Bader, R. F. W. Atoms in Molecules-A Quantum Theory; Oxford University Press: Oxford, UK. 1990.
63. [63]
  Seybold, P. G.; Shields, G. C. 2015, 5, 290. doi: 10.1002/wcms.1218
64. [64]
  Juranić, I. Croat. Chem. Acta 2014, 87 343. doi: org/10.5562/cca2462
65. [65]
  Zhou, X. Y.; Rong, C. Y.; Lu, T.; Liu, S. B. Acta Phys. -Chim. Sin. 2014, 20, 2055. doi: 10.3866/PKU.WHXB201409193
1. [1]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
2. [2]
  Jian Yang , Guang Yang , Zhijie Chen . Capturing carbon dioxide from air by using amine-functionalized metal-organic frameworks. Chinese Journal of Structural Chemistry, 2024, 43(5): 100267-100267. doi: 10.1016/j.cjsc.2024.100267
3. [3]
  Minghao Hu , Tianci Xie , Yuqiang Hu , Longjie Li , Ting Wang , Tongbo Wu . Allosteric DNAzyme-based encoder for molecular information transfer. Chinese Chemical Letters, 2024, 35(7): 109232-. doi: 10.1016/j.cclet.2023.109232
4. [4]
  Zixi Zou , Jingyuan Wang , Yian Sun , Qian Wang , Da-Hui Qu . Controlling molecular assembly on time scale: Time-dependent multicolor fluorescence for information encryption. Chinese Chemical Letters, 2024, 35(7): 108972-. doi: 10.1016/j.cclet.2023.108972
5. [5]
  Huijiao Fu , Peiqin Liang , Qianwen Chen , Yan Wang , Guang Li , Xuzi Cai , Shengtao Wang , Kun Chen , Shengying Shi , Zhiqiang Yu , Xuefeng Wang . COX-2 blocking therapy in cisplatin chemosensitization of ovarian cancer: An allicin-based nanomedicine approach. Chinese Chemical Letters, 2024, 35(8): 109241-. doi: 10.1016/j.cclet.2023.109241
6. [6]
  Bohan Zhang , Bingzhe Wang , Guichuan Xing , Zikang Tang , Songnan Qu . Regulation of the multi-emission centers in carbon dots via a bottom-up synthesis approach. Chinese Chemical Letters, 2024, 35(9): 109358-. doi: 10.1016/j.cclet.2023.109358
7. [7]
  Yaxian Liang , Qingyi Li , Liwei Hu , Ruohan Zhai , Fan Liu , Lin Tan , Xiaofei Wang , Huixu Xie . Environmentally friendly polylysine gauze dressing for an innovative antimicrobial approach to infected wound management. Chinese Chemical Letters, 2024, 35(10): 109459-. doi: 10.1016/j.cclet.2023.109459
8. [8]
  Yujia Shi , Yan Qiao , Pengfei Xie , Miaomiao Tian , Xingwei Li , Junbiao Chang , Bingxian Liu . Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach. Chinese Chemical Letters, 2024, 35(10): 109544-. doi: 10.1016/j.cclet.2024.109544
9. [9]
  Yunfei Shen , Long Chen . Gradient imprinted Zn metal anodes assist dendrites-free at high current density/capacity. Chinese Journal of Structural Chemistry, 2024, 43(10): 100321-100321. doi: 10.1016/j.cjsc.2024.100321
10. [10]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472
11. [11]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
12. [12]
  Huyi Yu , Renshu Huang , Qian Liu , Xingfa Chen , Tianqi Yu , Haiquan Wang , Xincheng Liang , Shibin Yin . Te-doped Fe3O4 flower enabling low overpotential cycling of Li-CO2 batteries at high current density. Chinese Journal of Structural Chemistry, 2024, 43(3): 100253-100253. doi: 10.1016/j.cjsc.2024.100253
13. [13]
  Aolei Tan , Xiaoxiao Ma . Exploring the functional roles of small-molecule metabolites in disease research: Recent advancements in metabolomics. Chinese Chemical Letters, 2024, 35(8): 109276-. doi: 10.1016/j.cclet.2023.109276
14. [14]
  Tianze Wang , Junyi Ren , Dongxiang Zhang , Huan Wang , Jianjun Du , Xin-Dong Jiang , Guiling Wang . Development of functional dye with redshifted absorption based on Knoevenagel condensation at 1-site in phenyl[b]-fused BODIPY. Chinese Chemical Letters, 2024, 35(6): 108862-. doi: 10.1016/j.cclet.2023.108862
15. [15]
  Xinyu Ren , Hong Liu , Jingang Wang , Jiayuan Yu . Electrospinning-derived functional carbon-based materials for energy conversion and storage. Chinese Chemical Letters, 2024, 35(6): 109282-. doi: 10.1016/j.cclet.2023.109282
16. [16]
  Guiyang Zheng , Xuelian Kang , Haoran Ye , Wei Fan , Christian Sonne , Su Shiung Lam , Rock Keey Liew , Changlei Xia , Yang Shi , Shengbo Ge . Recent advances in functional utilisation of environmentally friendly and recyclable high-performance green biocomposites: A review. Chinese Chemical Letters, 2024, 35(4): 108817-. doi: 10.1016/j.cclet.2023.108817
17. [17]
  Zeyu Jiang , Yadi Wang , Changwei Chen , Chi He . Progress and challenge of functional single-atom catalysts for the catalytic oxidation of volatile organic compounds. Chinese Chemical Letters, 2024, 35(9): 109400-. doi: 10.1016/j.cclet.2023.109400
18. [18]
  Jiajing Wu , Ru-Ling Tang , Sheng-Ping Guo . Three types of promising functional building units for designing metal halide nonlinear optical crystals. Chinese Journal of Structural Chemistry, 2024, 43(6): 100291-100291. doi: 10.1016/j.cjsc.2024.100291
19. [19]
  Xin Li , Wanting Fu , Ruiqing Guan , Yue Yuan , Qinmei Zhong , Gang Yao , Sheng-Tao Yang , Liandong Jing , Song Bai . Nucleophiles promotes the decomposition of electrophilic functional groups of tetracycline in ZVI/H₂O₂ system: Efficiency and mechanism. Chinese Chemical Letters, 2024, 35(10): 109625-. doi: 10.1016/j.cclet.2024.109625
20. [20]
  Haodong Wang , Xiaoxu Lai , Chi Chen , Pei Shi , Houzhao Wan , Hao Wang , Xingguang Chen , Dan Sun . Novel 2D bifunctional layered rare-earth hydroxides@GO catalyst as a functional interlayer for improved liquid-solid conversion of polysulfides in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108473-. doi: 10.1016/j.cclet.2023.108473

Get Citation

PDF

XML

Metrics

PDF Downloads(9)
Abstract views(665)
HTML views(44)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142