Abstract
The electron distribution of molecules with distorted aromatic rings was analyzed using theoretical methods. The molecular geometries of Dewar benzene, the series of [n]paracyclophanes (n = 2, \(\ldots\), 6), and [1.1] and [2.2]paracyclophane were optimized at the QCISD/6-31++G(d,p) approximation. The partition of three-dimensional space provided by the quantum theory of atoms in molecules was applied using the electron densities obtained at this highly correlated level of theory. The analysis shows that Dewar benzene and [2]paracyclophane belong in a separate family. In the other cases, the distortion of the benzene moiety provokes a charge transfer to the phenylene group and induces a moderate single bond–double bond alternation that yields some decrease in the aromaticity of the carbon backbone. The charge concentrations accounted for by the Laplacian of the electron density and the quadrupole polarization of the ipso C atoms provide an explanation for their reactivity in electrophilic substitution reactions. The steric strain in paracyclophanes was analyzed in terms of the forces exerted on the electron density, the Ehrenfest forces. This analysis did not provide any evidence of repulsive forces taking place in the molecules. In particular, the aromatic rings in [2.2]paracyclophane are highly aromatic, with an important electron delocalization between aromatic rings and forces that are always attractive.
Similar content being viewed by others
References
Tsuji T, Ohkita M, Kawai H (2002) Bull Chem Soc Jpn 75(3):415
Tsuji T (2004) In modern cyclophane chemistry. Wiley-VCH, chap. 3, pp 81–104
Tobe Y (1994) In cyclophanes. Springer, chap. 1, pp 1–40. Top Curr Chem 172
Zyss J, Ledoux I, Volkov S, Chernyak V, Mukamel S, Bartholomew GP, Bazan GC (2000) J Am Chem Soc 122(48):11956
Ghasemabadi PG, Yao T, Bodwell GJ (2015) Chem Soc Rev 44:6494
Cram DJ, Cram JM (1971) Acc Chem Res 4(6):204
Batra A, Kladnik G, Vzquez H, Meisner JS, Floreano L, Nuckolls C, Cvetko D, Morgante A, Venkataraman L (2012) Nat Commun 3:1086
Bally T, Matzinger S, Bednarek P (2006) J Am Chem Soc 128(24):7828
Dransk M, Castao O, Kotora M, Bou P (2010) J Org Chem 75(3):576
Havenith R, Jenneskens L, van Lenthe J (1999) J Mol Struc Theochem 492(1–3):217
Tsuji T, Nishida S (1987) J Chem Soc Chem Commun 1189–1190
Tsuji T, Nishida S (1988) J Am Chem Soc 110(7):2157
Kostermans GBM, Bobeldijk M, Wolf WHD, Bickelhaupt F (1987) J Am Chem Soc 109(8):2471
Hopf H (2012) Isr J Chem 52(1–2):18
Jenneskens LW, Havenith RWA, Soncini A, Fowler PW (2011) Phys Chem Chem Phys 13:16861
Bai M, Liang J, Xie L, Sanvito S, Mao B, Hou S (2012) J Chem Phys 136(10):104701
Lyssenko KA, Antipin MY, Antonov DY (2003) Chem Phys Chem 4(8):817
Bader RFW (1990) Atoms in molecules: a quantum theory. Clarendon Press, Oxford
Hope H, Bernstein J, Trueblood KN (1972) Acta Crystallogr Sect B Struct Sci 28:1733
Caramori GF, Galembeck SE, Laali KK (2005) J Org Chem 70(8):3242
Lyssenko KA, Korlyukov AA, Antipin MY (2005) Mendeleev Commun 15(3):90
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA,Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA,Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF,Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K,Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O,Nakai H, Vreven T, Montgomery JA Jr., Peralta JE, Ogliaro F,Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN,Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A,Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N,Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C,Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ,Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K,Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S,Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2013) Gaussian 09, revision d.01
Keith TA (2016) Aimall (version 16.01.09, professional). aim.tkgristmill.com
Elango M, Parthasarathi R, Subramanian V, Chattaraj P (2007) J Mol Struct Theochem 820(1–3):1
Caramori GF, Galembeck SE (2007) J Phys Chem A 111(9):1705
Feixas F, Matito E, Poater J, Solà M (2007) J Phys Chem A 111(20):4513
Carey FA, Sundberg RJ (2007) Advanced organic chemistry, 5th edn. Springer, New York
Matta CF, Hernández-Trujillo J (2003) J Phys Chem A 107(38):7496
Matta CF, Hernández-Trujillo J (2005) J Phys Chem A 109(47):10798
Farrugia LJ, Evans C, Tegel M (2006) J Phys Chem A 110(25):7952
Poater J, Duran M, Solà M, Silvi B (2005) Chem Rev 105(10):3911
Merino G, Vela A, Heine T (2005) Chem Rev 105(10):3812
Feixas F, Matito E, Poater J, Solà M (2015) Chem Soc Rev 44:6434
Feixas F, Vandenbussche J, Bultinck P, Matito E, Solà M (2011) Phys Chem Chem Phys 13:20690
Bickelhaupt F, de Wolf WH (1998) J Phys Org Chem 11(5):362
Bader RFW, Chang C (1989) J Phys Chem 93(8):2946
Moa MJG, Mosquera RA (2006) J Phys Chem A 110(17):5934
Cortés-Guzmán F, Bader RFW (2005) Coord Chem Rev 249(56):633
Dijkstra F, Van Lenthe JH (1999) Int J Quantum Chem 74(2):213
Tsuji T, Okuyama M, Ohkita M, Kawai H, Suzuki T (2003) J Am Chem Soc 125(4):951
Poater J, Bofill JM, Alemany P, Solà M (2006) J Org Chem 71(4):1700
Dobrowolski MA, Cyranski MK, Wrobel Z (2016) Phys Chem Chem Phys 18:11813
Poater J, Fradera X, Duran M, Solà M (2003) Chem Eur J 9(2):400
Bultinck P, Rafat M, Ponec R, Gheluwe BV, Carbó-Dorca R, Popelier P (2006) J Phys Chem A 110(24):7642
Garcia-Revilla M, Hernandez-Trujillo J (2009) Phys Chem Chem Phys 11:8425
Estevez-Fregoso M, Hernandez-Trujillo J (2016) Phys Chem Chem Phys
Matito E, Poater J, Duran M, Solà M (2005) J Mol Struct Theochem 727(1–3):165
Ernst L (2000) Prog Nucl Magn Reson Spectrosc 37:47
Gillespie R, Popelier P (2001) Chemical bonding and molecular geometry: from lewis to electron densities. Oxford University Press, Oxford
Hernández-Trujillo J, García-Cruz I, Martínez-Magadán JM (2005) Chem Phys 308(1–2):181
Pendas AM (2002) J Chem Phys 117(3):965
Bader RFW, Fang DC (2005) J Chem Theor Comput 1(3):403
Martín A (2012) Pendás. J Chem Phys 137(13):134101
Maza JR, Jenkins S, Kirk SR, Anderson JSM, Ayers PW (2013) Phys Chem Chem Phys 15:17823
Cortés-Guzmán F, Cuevas G, Martín Pendás A (2015) J Hernández-Trujillo Phys Chem Chem Phys 17:19021
Hernández Trujillo J, Cortés-Guzmán F, Fang DC, Bader RFW (2007) Faraday Discuss 135:79
Grimme S (2004) Chem Eur J 10(14):3423
Acknowledgments
The author thanks Bruno Landeros-Rivera for his useful comments and suggestions.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published as part of the special collection of articles “Festschrift in honour of A. Vela”.
The author gratefully thanks DGTIC-UNAM for supercomputer resources (Project SC16-1-IR-71) and UNAM-DGAPA-PAPIIT (Project IN115215) for financial support.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Hernández-Trujillo, J. Electron density analysis of bent aromatic molecules: intramolecular interactions in small paracyclophanes. Theor Chem Acc 135, 198 (2016). https://doi.org/10.1007/s00214-016-1960-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-016-1960-3