运用密度泛函活性理论的信息论方法研究苯并富烯衍生物的芳香性

doi:10.3866/PKU.WHXB201710231

Abstract

Abstract:

Although a large variety of aromatic systems have been unveiled in the literature, justifying their origin of stability and understanding their nature of aromaticity is still an unaccomplished task. In this work, using tools recently developed by us within the density functional reactivity theory framework, where we employ simple density functionals to quantify molecular structural and reactivity properties, we examine the aromaticity concept from a different perspective. Using six quantities from the information-theoretic approach, namely, the Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy, Onicescu information energy, information gain, and relative Rényi entropy, and four aromaticity descriptors, namely, the aromatic stabilization energy (ASE) index, the harmonic oscillator model of aromaticity (HOMA) index, the aromatic fluctuation (FLU) index, and the nucleus-independent chemical shift (NICS) index, we systematically examined the correlations between substituted fulvene derivatives fused with one, two, and three benzene rings. Among the 14 benzofulvene derivatives studied in this work, there were seven single-fused, four double-fused, and three triple-fused benzofulvene derivatives. Our results show that the aromaticity indexes are often well correlated with one another. The same is true for information-theoretic quantities. Moreover, these correlations are valid across all series of benzofulvene derivatives with different ring structures. The cross-correlations between information-theoretic quantities and aromaticity indexes were usually strong. However, two completely opposite patterns were observed; as a consequence, these correlations are not valid across all series of benzofulvene derivatives. The nature of these correlations depends on the nature of the ring structure. The two groups of systems, each obeying the same cross-correlation patterns, have a total number of 4n + 2 and 4n π electrons, respectively, which are in agreement with Hückel's rule of aromaticity and antiaromaticity. Compared with the results obtained for systems without a benzene fused ring, the correlation patterns of these quantities were always found to be the same, both with and without fused benzene rings. This suggests that, despite benzene's aromaticity, its fusion with a fulvene moiety does not modify the aromaticity and antiaromaticity of the fulvene ring. These results confirm that the fusion of benzene rings with a fulvene moiety has no influence on the aromatic nature of the fulvene moiety. Thus, the aromaticity and antiaromaticity of benzene-fused fulvene derivatives are solely determined by the fulvene moiety. These results should provide a new understanding of the origin and nature of aromaticity and antiaromaticity.

Key words: Aromaticity, Antiaromaticity, Benzofulvene, Information-theoretic approach, Density functional reactivity theory

Donghai. YU,Chunying. RONG,Tian. LU,Frank. DE PROFT,Shubin. LIU. Aromaticity Study of Benzene-Fused Fulvene Derivatives Using the Information-Theoretic Approach in Density Functional Reactivity Theory[J]. Acta Phys. -Chim. Sin. 2018, 34(6), 639-649. doi: 10.3866/PKU.WHXB201710231

References

1	Solà M. Front. Chem. 2017, 5, 1.
2	Herndon W. C. ; Mills N. S. J. Org. Chem. 2005, 70, 8492.
3	Skov A. B. ; Broman S. L. ; Gertsen A. S. ; Elm J. ; Jevric M. ; Cacciarini M. ; Kadziola A. ; Mikkelsen K. V. ; Nielsen M. B. Chem. -Eur. J. 2016, 22, 14567.
4	Aihara J. -I. J. Am. Chem. Soc. 2006, 128, 2873.
5	Cyrański M. K. Chem. Rev. 2005, 105, 3773.
6	Feixas F. ; Matito E. ; Poater J. ; Solà M. Chem. Soc. Rev. 2015, 44, 6434.
7	Sumita A. ; Gasonoo M. ; Boblak K. J. ; Ohwada T. ; Klumpp D. A. Chem. -Eur. J. 2017, 23, 2566.
8	Szczepanik D. W. ; Solà M. ; Andrzejak M. ; Pawe?ek B. ; Dominikowska J. ; Kuku?ka M. ; Dyduch K. ; Krygowski T. M. ; Szatylowicz H. J. Comput. Chem. 2017, 38, 1640.
9	Liu J. Z. ; Ma J. ; Zhang K. ; Ravat P. ; Machata P. ; Avdoshenko S. ; Hennersdorf F. ; Komber H. ; Pisula W. Weigand J. J., et al. J. Am. Chem. Soc. 2017, 139, 7513.
10	Yoon Z. S. ; Osuka A. ; Kim D. Nat. Chem. 2009, 1, 113.
11	Frederickson C. K. ; Zakharov L. N. ; Haley M. M. J. Am. Chem. Soc. 2016, 138, 16827.
12	Boldyrev A. I. ; Popov I. A. ; Starikova A. A. ; Steglenko D. V. Chem. -Eur. J. 2017.
13	Marcos E. ; Anglada J. M. ; Torrent-Sucarrat M. J. Org. Chem. 2014, 79, 5036.
14	St?pień M. ; Latos-Gra?yński L. ; Sprutta N. ; Chwalisz P. ; Szterenberg L. Angew. Chem. 2007, 119, 8015.
15	Szyszko B. ; Sprutta N. ; Chwalisz P. ; St?pień M. ; Latos-Gra?yński L. Chem. -Eur. J. 2014, 20, 1985.
16	Mobius K. ; Plato M. ; Klihm G. ; Laurich C. ; Savitsky A. ; Lubitz W. ; Szyszko B. ; Stepien M. ; Latos-Grazynski L. Phys. Chem. Chem. Phys. 2015, 17, 6644.
17	M?bius K. ; Savitsky A. ; Lubitz W. ; Plato M. Appl. Magn. Reson. 2016, 47, 757.
18	Marcos E. ; Anglada J. M. ; Torrent-Sucarrat M. J. Phys. Chem. C 2012, 116, 24358.
19	Rosenberg M. ; Dahlstrand C. ; Kils K. ; Ottosson H. Chem. Rev. 2014, 114, 5379.
20	Ottosson H. Nat. Chem. 2012, 4, 969.
21	Liew J. Y. ; Brown J. J. ; Moore E. G. ; Schwalbe M. Chem. -Eur. J. 2016, 22, 16178.
22	Naskar S. ; Das M. ACS Omega 2017, 2, 1795.
23	van Leeuwen T. ; Pol J. ; Roke D. ; Wezenberg S. J. ; Feringa B. L. Org. Lett. 2017, 19, 1402.
24	Feixas F. ; Matito E. ; Poater J. ; Solà M. WIREs: Comput. Mol. Sci. 2013, 3, 105.
25	Bühl M. ; Hirsch A. Chem. Rev. 2001, 101, 1153.
26	El Bakouri O. ; Duran M. ; Poater J. ; Feixas F. ; Sola M. Phys. Chem. Chem. Phys. 2016, 18, 11700.
27	Zhu C. Q. ; Yang C. X. ; Wang Y. H. ; Lin G. ; Yang Y. H. ; Wang X. Y. ; Zhu J. ; Chen X. Y. ; Lu X. ; Liu G. ;et al Sci. Adv. 2016, 2, e1601031.
28	Ayub R. ; Bakouri O. E. ; Jorner K. ; Solà M. ; Ottosson H. J. Org. Chem. 2017, 82, 6327.
29	Suzuki S. ; Morita Y. ; Fukui K. ; Sato K. ; Shiomi D. ; Takui T. ; Nakasuji K. J. Am. Chem. Soc. 2006, 128, 2530.
30	Chen Z. F. ; Wannere C. S. ; Corminboeuf C. ; Puchta R. ; von Ragué Schleyer P. Chem. Rev. 2005, 105, 3842.
31	Schleyer P. v. R. ; Maerker C. ; Dransfeld A. ; Jiao H. ; van Eikema Hommes N. J. R. J. Am. Chem. Soc. 1996, 118, 6317.
32	Fallah-Bagher-Shaidaei H. ; Wannere C. S. ; Corminboeuf C. ; Puchta R. ; Schleyer P. v. R. Org. Lett. 2006, 8, 863.
33	Krygowski T. M. ; Szatylowicz H. ; Stasyuk O. A. ; Dominikowska J. ; Palusiak M. Chem. Rev. 2014, 114, 6383.
34	Poater J. ; Fradera X. ; Duran M. ; Solà M. Chem. -Eur. J. 2003, 9, 400.
35	Matito E. ; Duran M. ; Solà M. J. Chem. Phys. 2005, 122, 014109.
36	Hong Y. ; Oh J. ; Sung Y. M. ; Tanaka Y. ; Osuka A. ; Kim D. Angew. Chem. Int. Ed. 2017, 56, 2932.
37	Feixas F. ; Matito E. ; Poater J. ; Solà M. J. Comput. Chem. 2008, 29, 1543.
38	Yu D. H. ; Rong C. Y. ; Lu T. ; Chattaraj P. K. ; De Proft F. ; Liu S. B. Phys. Chem. Chem. Phys. 2017, 19, 18635.
39	Liu S. B. Acta Phys. -Chim. Sin. 2016, 32, 98.
40	Liu S. B. Acta Phys. -Chim. Sin. 2009, 25, 590.
41	Zhao L. L. ; Grande-Aztatzi R. ; Foroutan-Nejad C. ; Ugalde J. M. ; Frenking G. ChemistrySelect 2017, 2, 863.
42	Ciesielski A. ; Krygowski T. M. ; Cyranski M. K. ; Balaban A. T. Phys. Chem. Chem. Phys. 2011, 13, 3737.
43	Bernasconi C. F. ; Wenzel P. J. J. Org. Chem. 2010, 75, 8422.
44	Mo Y. R. ; Schleyer P. v. R. Chem. -Eur. J. 2006, 12, 2009.
45	Gershoni-Poranne R. ; Stanger A. Chem. Soc. Rev. 2015, 44, 6597.
46	De Oliveira B. G. Phys. Chem. Chem. Phys. 2013, 15, 37.
47	Zhu J. ; An K. ; Schleyer P. v. R. Org. Lett. 2013, 15, 2442.
48	Cyra?ski M. K. ; Krygowski T. M. ; Katritzky A. R. ; Schleyer P. v. R. J. Org. Chem. 2002, 67, 1333.
49	Krygowski T. M. ; Cyrański M. K. Chem. Rev. 2001, 101, 1385.
50	Alvarez-Thon L. ; Mammino L. Int. J. Quantum Chem. 2017, 117, e25382.
51	Karadakov P. B. ; Hearnshaw P. ; Horner K. E. J. Org. Chem. 2016, 81, 11346.
52	Boll M. ; Hilker T. A. ; Salomon G. ; Omran A. ; Nespolo J. ; Pollet L. ; Bloch I. ; Gross C. Science 2016, 353, 1257.
53	Sundholm D. ; Fliegl H. ; Berger R. J. F. WIREs: Comput. Mol. Sci. 2016, 6, 639.
54	Liu S. B. J. Chem. Phys. 2007, 126, 191107.
55	Liu S. B. ; Rong C. Y. ; Wu Z. M. ; Lu T. Acta Phys. -Chim. Sin. 2015, 2057
56	Noorizadeh S. ; Shakerzadeh E. Comput. Theor. Chem. 2011, 964, 141.
57	M?llerstedt H. ; Piqueras M. C. ; Crespo R. ; Ottosson H. J. Am. Chem. Soc. 2004, 126, 13938.
58	Becke A. D. J. Chem. Phys. 1993, 98, 5648.
59	Lee C. ; Yang W. ; Parr R. G. Phys. Rev. B 1988, 37, 785.
60	Francl M. M. ; Pietro W. J. ; Hehre W. J. ; Binkley J. S. ; Gordon M. S. ; DeFrees D. J. ; Pople J. A. J. Chem. Phys. 1982, 77, 3654.
61	Rassolov V. A. ; Ratner M. A. ; Pople J. A. ; Redfern P. C. ; Curtiss L. A. J. Comput. Chem. 2001, 22, 976.
62	Frisch M. J. ; Trucks G. W. ; Schlegel H. B. ; Scuseria G. E. ; Robb M. A. ; Cheeseman J. R. ; Scalmani G. ; Barone V. ; Mennucci B. ; Petersson G. A. et al Gaussian 09, Revision E. 01 Gaussian Inc.: Wallingford, CT, USA, 2013.
63	Kudin K. N. ; Scuseria G. E. ; Cancès E. J. Chem. Phys. 2002, 116, 8255.
64	Lu T. ; Chen F. W. J. Comput. Chem. 2012, 33, 580.
65	Becke A. D. J. Chem. Phys. 1988, 88, 2547.
66	Richard F. ; Bader R. Atoms in Molecules: a Quantum Theory; Oxford University Press, Oxford, UK 1990.
67	Hirshfeld F. L. Theor. Chim. Acta 1977, 44, 129.
68	Zhou X. Y. ; Rong C. Y. ; Lu T. ; Liu S. B. Acta Phys. -Chim. Sin. 2014, 30, 2055.
69	Liu S. B. J. Phys. Chem. A 2015, 119, 3107.
70	Kohn W. ; Sham L. J. Phys. Rev. 1965, 140, A1133.
71	Zhao D. B. ; Rong C. Y. ; Ying D. L. ; Liu S. B. J. Theor. Comput. Chem. 2013, 12, 1350034.
72	Wu W. J. ; Wu Z. M. ; Rong C. Y. ; Lu T. ; Huang Y. ; Liu S. B. J. Phys. Chem. A 2015, 119, 8216.
73	Wu Z. M. ; Rong C. Y. ; Lu T. ; Ayers P. W. ; Liu S. B. Phys. Chem. Chem. Phys. 2015, 17, 27052.
74	Huang Y. ; Rong C. Y. ; Zhang R. Q. ; Liu S. B. J. Mol. Model. 2016, 23, 3.
75	Liu S. B. ; Rong C. Y. ; Lu T. Phys. Chem. Chem. Phys. 2017, 19, 1496.
76	Zhou X. Y. ; Rong C. Y. ; Lu T. ; Zhou P. P. ; Liu S. B. J. Phys. Chem. A 2016, 120, 3634.
77	Noorizadeh S. ; Shakerzadeh E. Phys. Chem. Chem. Phys. 2010, 12, 4742.
78	Snyder G. J. J. Phys. Chem. A 2012, 116, 5272.
79	Halton B. Eur. J. Org. Chem. 2005, 2005, 3391.

[1]	Yanfang SHEN,Longjiu CHENG. Electronic Stability of Eight-electron Tetrahedral Pd₄ Clusters [J]. Acta Phys. -Chim. Sin., 2018, 34(7): 830-836.
[2]	Shu-Bin LIU. Information-Theoretic Approach in Density Functional Reactivity Theory [J]. Acta Phys. -Chim. Sin., 2016, 32(1): 98-118.
[3]	Shu-Bin. LIU,Chun-Ying. RONG,Ze-Min. WU,Tian. LU. Rényi Entropy, Tsallis Entropy and Onicescu Information Energy in Density Functional Reactivity Theory [J]. Acta Phys. -Chim. Sin., 2015, 31(11): 2057-2063.
[4]	LIU Liang-Hong, ZHANG Peng-Fei, HUANG Ying. Molecular Acidity of Singly and Doubly Substituted Phenols: Predictions from Density Functional Reactivity Theory and Hammett Constants [J]. Acta Phys. -Chim. Sin., 2013, 29(03): 508-515.
[5]	WU Lin-Feng, LI Fei-Fei, ZHANG Cong-Jie. Structure and Stability of Compounds with Planar Pentacoordinate Carbons and Planar Tetracoordinate Carbons [J]. Acta Phys. -Chim. Sin., 2012, 28(05): 1113-1119.
[6]	XU Hui-Ying, WANG Wei. Interaction between Mg-Porphyrin and Nitrogen, Oxygen Heterocyclic Compounds [J]. Acta Phys. -Chim. Sin., 2011, 27(11): 2565-2570.
[7]	LIU Yu-Ning, LIU Zi-Zhong, LI Wei-Qi, LIU Dong-Sheng, GE Xiang-Wei. Structures and Aromaticities of Complexes (1,3,5-C₃P₃H₃)M and (1,3,5-C₃P₃H₃)₂M (M=Ti, V, Cr) [J]. Acta Phys. -Chim. Sin., 2011, 27(10): 2282-2290.
[8]	GONG Liang-Fa, WU Xin-Min, LI Wei, QI Chuan-Song. Stability and Aromaticity of XB₆⁺ (X=C, Si, Ge, Sn, Pb) Clusters [J]. Acta Phys. -Chim. Sin., 2011, 27(04): 831-836.
[9]	LIANG Jing-Xia, JIA Wen-Hong, ZHANG Cong-Jie, CAO Ze-Xing. Unusual Boron-Carbon Compounds Containing Planar Tetracoordinate and Pentacoordinate Carbons [J]. Acta Phys. -Chim. Sin., 2009, 25(09): 1847-1852.
[10]	WANG Wei, SHAO Shi-Qun, ZHOU Hui, TENG Qi-Wen. Molecular Recognition and Spectroscopic Properties of Cyclobis(paraquat-p-anthracene) [J]. Acta Phys. -Chim. Sin., 2008, 24(09): 1631-1636.
[11]	QIU Wei-Wei; LIN Meng-Hai. Aromaticity of Transition-Metal Clusters Nb_n, Co_n (n≤4) and NbxCoy (x+y≤8) [J]. Acta Phys. -Chim. Sin., 2008, 24(09): 1573-1578.
[12]	LI Zhi-Wei; ZHAO Cun-Yuan; CHEN Liu-Ping. Structures and Aromaticities of As^-₅, [As₅M]^-, and [As₅MAs₅]^2-(M=Ti, Zr, Hf) [J]. Acta Phys. -Chim. Sin., 2008, 24(05): 755-759.
[13]	SUN Wen-Xiu; ZHANG Cong-Jie. ATheoretical Study on a Kind of Novel Diboron Organic Compound with a Planar Tetracoordinate Carbon [J]. Acta Phys. -Chim. Sin., 2008, 24(01): 32-36.
[14]	Zhou Li-Xin, Mang Chao-Yong, Zhang Yong-Fan. Gas-phase Acidity and Aromaticity of 1,2-dithiosquaric Acid [J]. Acta Phys. -Chim. Sin., 2000, 16(01): 15-21.

Aromaticity Study of Benzene-Fused Fulvene Derivatives Using the Information-Theoretic Approach in Density Functional Reactivity Theory

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 14

Metrics

Recommended 0