Do Special Noncovalent π–π Stacking Interactions Really Exist?

Angewandte Chemie International EditionVolume 47, Issue 18 p. 3430-3434 Communication Do Special Noncovalent π–π Stacking Interactions Really Exist?† Stefan Grimme Prof. Dr., Stefan Grimme Prof. Dr. [email protected] Theoretische Organische Chemie, Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-83-36515Search for more papers by this author Stefan Grimme Prof. Dr., Stefan Grimme Prof. Dr. [email protected] Theoretische Organische Chemie, Organisch-Chemisches Institut, Universität Münster, Corrensstrasse 40, 48149 Münster, Germany, Fax: (+49) 251-83-36515Search for more papers by this author First published: 14 April 2008 https://doi.org/10.1002/anie.200705157Citations: 875 † This work was supported by the Deutsche Forschungsgemeinschaft as part of the SFB 424 (“Molekulare Orientierung als Funktionskriterium in chemischen Systemen”). The author thanks C. Mück-Lichtenfeld for technical assistance and J. Antony for helpful discussions. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Van der Waals complexes are formed by almost all neutral molecules, which begs the question as to what is so special about the interaction between parallel stacks of arenes. The term π–π stacking interactions should primarily be used as a structural descriptor for unsaturated systems. Genuine π–π interactions are caused by specific electron correlations that are only at work for short intermolecular distances. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z705157_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1J.-M. Lehn, Supramolecular Chemistry. Concepts and Perspectives, VCH, Weinheim, 1995; E. A. Meyer, R. K. Castellano, F. Diederich, Angew. Chem. 2003, 115, 1244–1287; Angew. Chem. Int. Ed. 2003, 42, 1210–1250; N. Kannan, S. Vishveshwara, Protein Eng. 2000, 13, 753–761; P. Hobza, J. Šponer, Chem. Rev. 1999, 99, 3247–3276; K. Müller-Dethlefs, P. Hobza, Chem. Rev. 2000, 100, 143–167; K. S. Kim, P. Tarakeshwar, J. Y. Lee, Chem. Rev. 2000, 100, 4145–4185; J. Cerny, P. Hobza, Phys. Chem. Chem. Phys. 2007, 9, 5291–5303. 2M. O. Sinnokrot, C. D. Sherrill, J. Phys. Chem. 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Schwabe, S. Grimme, Phys. Chem. Chem. Phys. 2007, 9, 3397–3406. 22S. Grimme, J. Chem. Phys. 2003, 118, 9095–9102. 23NIST Standard Reference Database. See http://webbook.nist.gov/chemistry/. 24K. Morokuma, J. Chem. Phys. 1971, 55, 1236–1244. 25One should be careful when interpreting Pauli-exchange repulsion and electrostatic components separately, because they are derived from an nonphysical state of the system that is not antisymmetric with respect to interchange of electron coordinates. This does not hold for E1, which is thus mainly discussed. 26S. Grimme, Angew. Chem. 2006, 118, 4571–4575; Angew. Chem. Int. Ed. 2006, 45, 4460–4464. 27The dispersion-corrected DFT-D methods without the PT2 part (almost independent of the actual density functional used), although being quite accurate for the absolute interaction energies of the aromatic systems, fail on the correct discrimination of the larger aromatic versus saturated stacked dimers (see Figure 2 in the Supporting Information). However, only small consequences arise for, for example, the computed structures with B97-D that are accurate to within a few pm for the intermolecular distances, even if a somewhat deficient dispersion energy is used. In the conventional DFT-D approach, further improvement can only be achieved by hybridization-specific atomic (i.e., sp2 vs. sp3 carbon) C6 parameters. 28One simple reason why stacking of saturated systems is not so frequently observed is that lateral displacement (as for example, forced by the surroundings) leads directly to a strong distortion of the interlocked saturated structure, whereas the aromatic fragments can more easily slide against each other. This effect also leads to unfavorable entropies. 29S. Grimme, Chem. Eur. J. 2004, 10, 3423–3429. 30R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165–169; TURBOMOLE, version 5.9: R. Ahlrichs et al., Universität Karlsruhe 2006. See http://www.turbomole.com. See the Supporting Information for a full list of authors. 31A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829–5835; F. Weigend, F. Furche, R. Ahlrichs, J. Chem. Phys. 2003, 119, 12753–12762. The basis sets are available from the TURBOMOLE homepage via the FTP Server Button (in the subdirectories basen, jbasen, and cbasen). See http://www.turbomole.com. 32J. Antony, S. Grimme, J. Phys. Chem. A 2007, 111, 4862–4868. 33This (theoretically unsatisfactory) approach is motivated by the fact that MP2 is very close to CCSD(T) results for alkane dimer interactions, whereas the same holds for SCS-MP2 in the case of aromatic interactions; see reference [32] for details. Citing Literature Volume47, Issue18April 21, 2008Pages 3430-3434 ReferencesRelatedInformation