Abstract
The effects of chlorine substituents (Cl substituents) on the structural and electronic properties of lichexanthones (LXs) such as aromaticity of rings, the intramolecular interactions and the complexation of LXs with Mg2+ and NH3 (the ionic and halogen bond interactions) have been investigated by the quantum mechanical calculations at the M06-2X/6-311++G(d,p) level of theory. The effects of Cl substituents on the intramolecular H-bond interactions strongly depend on their positions on the ring. The Cl substituents increase the E2 values of nX → π*CC interactions, obtained from the natural bond orbital analysis, reduce the electron densities on the center of the substituted ring, ρRCP in the results of atoms in molecules analysis, and decrease the aromaticity of the rings with respect to the aromatic fluctuation index. The stabilities of compounds depend on the aromaticity of rings, the O···H-bond strength, and especially the Cl···H interaction. Also, the effects of substituents on the local minimum values of electrostatic potential around the O atoms (Vmin) and therefore the binding energies of [LX···Mg]2+ and [LX···Mg·4H2O]2+ complexes strongly depend on the positions of the substituents. The aromaticity of rings A and C decrease and that of B increases after complexation with the Mg2+ ion. The electronic effects (and in some cases the steric effects) play a special role in the formation and stability of LX···NH3 complexes. The stabilities of the LX···NH3 complexes increase by increasing the natural charges and the local maximum electrostatic potential (Vmax−Cl) calculated, respectively, on and around the Cl atoms, and the ρCl−N values calculated at the Cl···N BCPs.
Similar content being viewed by others
References
Verma AK, Pratap R (2010) Nat Prod Rep 27:1571
Crozier A, Jaganath IB, Clifford MN (2009) Nat Prod Rep 26:1001
Gaspar A, Matos MJ, Garrido J, Uriarte E, Borges F (2013) Chem Rev 114:4960
Ellis GP (1977) Chromenes, Chromanones, and Chromones, vol 31. Wiley, New York, p 1
Liu Y, Ma L, Chen WH, Park H, Ke Z, Wang B (2013) J Phys Chem B 117:13464
Shin Y, Han S, De U, Park J, Sharma S, Mishra NK, Lee EK, Lee Y, Kim HS, Kim IS (2014) J Org Chem 79:9262
Thong NM, Quang DT, Bui NHT, Dao DQ, Nam PC (2015) Chem Phys Lett 625:30
Hou C (2014) Comput Theor Chem 1028:87
Wang Y, Xia Z, Xu JR, Wang YX, Hou LN, Qiu Y, Chen HZ (2012) Neuropharmacology 62:871
Dzoyem JP, Lannang AM, Fouotsa H, Mbazoa CD, Nkengfack AE, Sewald N, Eloff JN (2015) Phytochem Lett 14:153
Wu Y, Hu M, Yang L, Li X, Bian J, Jiang F, Sun H, You Q, Zhang X (2015) Bioorg Med Chem Lett 25:2584
Teixeira C, Vale N, Pérez B, Gomes A, Gomes JRB, Gomes P (2014) Chem Rev 114:11164
Bernal FA, Coy-Barrera E (2015) Molecules 20:13165
Walgren RA, Walle UK, Walle T (1998) Biochem Pharmacol 55:1721
Walle T, Otake Y, Brubaker JA, Walle UK, Halushka PV (2001) J Clin Pharmacol 51:143
Chen AY, Chen CY (2013) Food Chem 138:2099
Walle T (2007) Mol Pharm 4:826
Manach C, Donovan JL (2004) Free Radical Res 38:771
Lalatsa A, Schatzlein AG, Uchegbu IF (2014) Mol Pharm 11:1081
Chae SW, Woo S, Park JH, Kwon Y, Na Y, Lee HJ (2015) Eur J Med Chem 93:237
Auffinger P, Hays FA, Westhof E, Ho PS (2004) Proc Natl Acad Sci USA 101:16789
Wang Y, Zeng Y, Li X, Meng L, Zhang X (2016) Struct Chem 27:1427
Wang W, Ji B, Zhang Y (2009) J Phys Chem A 113:8132
George J, Deringer VL, Dronskowski R (2014) J Phys Chem A 118:3193
Ren J, He Y, Chen W, Chen T, Wang G, Wang Z, Xu Z, Luo X, Zhu W, Jiang H, Shen J, Xu Y (2014) J Med Chem 57:3588
Ibrahim MAA (2011) J Comput Chem 32:2564
Masters KS, Bräse S (2012) Chem Rev 112:3717
Hussain H, Al-Harrasi A, Al-Rawahi A, Green IR, Gibbons S (2014) Chem Rev 114:10369
Nakashima KI, Tanaka T, Murata H, Kaburagi K, Inoue M (2015) Bioorg Med Chem Lett 25:1998
Tantapakul C, Maneerat W, Sripisut T, Ritthiwigrom T, Andersen RJ, Cheng P, Cheenpracha S, Raksat A, Laphookhieo S (2016) J Agric Food Chem 64:755
Sriyatep T, Andersen RJ, Patrick BO, Pyne SG, Muanprasat C, Seemakhan S, Borwornpinyo S, Laphookhieo S (2017) J Nat Prod 80:1658
Rapacz A, Sapa J, Nowiński L, Mogilski S, Pytka K, Filipek B, Siwek A, Szkaradek N, Marona H (2015) Pharmacol Rep 67:267
Robinson R (1955) Structural Relations of Natural Products. Oxford University Press, London, p 45
Oldenberg T, Wilkes H, Horsfield B, Van Duin A, Stoddart D, Willhelms A (2002) Org Geochem 33:595
Asahina Y, Nogami H (1942) Bull Chem Soc Jpn 17:202
Asahina Y, Shibata S (1954) Chemistry of lichen substances. Japan Society for the Promotion of Science, Tokyo, p 165
Krauser S, Hoffmann T, Heinzle E (2015) ACS Catal 5:1407
Cesaretti A, Carlotti B, Gentili PL, Clementi C, Germani R, Elisei F (2014) J Phys Chem B 118:8601
García-Fernández J, Trapiella-Alfonso L, Costa-Fernández JM, Pereiro R, Sanz-Medel A (2014) J Agric Food Chem 62:1733
Deshayes S, Xian W, Schmidt NW, Kordbacheh S, Lieng J, Wang J, Zarmer S, Germain SS, Voyen L, Thulin J, Wong GCL, Kasko AM (2017) Bioconjug Chem 28:793
Nicolás I, Vilchis M, Aragón N, Miranda R, Hojer G, Castro M (2003) Int J Quantum Chem 93:411
Brandelli A, Bizani D, Martinelli M, Stefani V, Gerbase AE (2004) Braz J Pharm Sci 40:247
Bonneau E, Legault P (2014) Biochemistry 53:579
Bauzá A, Ramis R, Frontera A (2014) J Phys Chem A 118:2827
Wang L, Gao J, Bi F, Song B, Liu C (2014) J Phys Chem A 118(39):9140
Gutten O, Beššeová I, Rulíšek L (2011) J Phys Chem A 115:11394
Gutten O, Rulíšek L (2013) Inorg Chem 52:10347
Falceto A, Theopold KH, Alvarez S (2015) Inorg Chem 54:10966
Li G, Yang H, Li F, Cheng F, Shi W, Chen J, Cheng P (2016) Inorg Chem 55:4935
Bader RFW (1990) Atoms in Molecules A Quantum Theory. Oxford University Press, Oxford
Reed AE, Curtiss AL, Weinhold F (1988) Chem Rev 88:899
Ozimiński WP, Dobrowolski JC (2009) J Phys Org Chem 22:769–778
Stanger A (2006) J Org Chem 71:883
Kumar C, Fliegl H, Sundholm D (2017) J Phys Chem A 121:7282
Portella G, Poater J, Solà M (2005) J Phys Org Chem 18:785
Zhao Y, Truhlar DG (2008) Theor Chem Acc 120:215
Krishnan R, Binkley JS, Seeger R, Pople JA (1980) J Chem Phys 72:650
Frisch MJ et al (2009) Gaussian 09, Revision A.02. Gaussian Inc., Wallingford
Becke AD (1993) J Chem Phys 98:5648
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785
Grimme S (2004) J Comput Chem 25:1463
Grimme S, Antony J, Ehrlich S, Krieg H (2010) J Chem Phys 132:154104
Dunning TH (1989) J Chem Phys 90:1007
Miertus S, Scrocco E, Tomasi J (1981) Chem Phys 55:117
Cossi M, Barone V, Cammi R, Tomasi J (1996) Chem Phys Lett 255:327
Boys SF, Bernardi F (1970) Mol Phys 19:553
Tommaso DD, De Leeuw NH (2010) Phys Chem Chem Phys 12:894–901
Dudev T, Lim C (2013) J Am Chem Soc 135:17200–17208
Biegler KF, Schonbohm J, Bayles D (2001) J Comput Chem 22:545
Glendening ED, Reed AE, Carpenter JE, Weinhold F (1990) NBO 3.0 Program Manual, Theoretical Chemistry Institute, University of Wisconsin, Madison
Lu T, Chen F (2012) J Comput Chem 33:580
Ritter SK (2015) Chem Eng News 93:37
Kleinpeter E, Koch A (2011) Phys Chem Chem Phys 13:20593
Kleinpeter E, Koch A (2012) Phys Chem Chem Phys 14:8742
Matito E, Duran M, Sola M (2005) J Chem Phys 122:014109
Güell M, Poater J, Luis JM, Mó O, YáÇez M, Solá M (2005) Chem Phys Chem 6:2552
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Mostafavi, N., Ebrahimi, A. The role of chlorine substituents in lichexanthones properties: the ionic and halogen bond interactions. Theor Chem Acc 137, 117 (2018). https://doi.org/10.1007/s00214-018-2294-0
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-018-2294-0