Characteristics of a σ-Hole and the Nature of a Halogen Bond
The nature of halogen bonding in 128 complexes was investigated using advanced quantum mechanical calculations. First, isolated halogen donors were studied and their σ-holes were described in terms of size and magnitude. Later, both partners in the complex were considered and their interaction was described in terms of DFT-SAPT decomposition. The whole set of complexes under study was split into two categories on the basis of their stabilisation energy. The first subset with 38 complexes possesses stabilisation energies in the range 7–32 kcal/mol, while the second subset with 90 complexes has stabilisation energies smaller than 7 kcal/mol. The first subset is characterised by small intermolecular distances (less than 2.5 Å) and a significant contraction of van der Waals (vdW) distance (sum of vdW radii). Here the polarisation/electrostatic energy is dominant, mostly followed by induction and dispersion energies. The importance of induction energy reflects the charge-transfer character of the respective halogen bonds. Intermolecular distances in the second subset are large and the respective contraction of vdW distance upon the formation of a halogen bond is much smaller. Here the dispersion energy is mostly dominant, followed by polarisation and induction energies. Considering the whole set of complexes, we conclude that the characteristic features of their halogen bonds arise from the concerted action of polarisation and dispersion energies and neither of these energies can be considered as dominant. Finally, the magnitude of the σ-hole and DFT-SAPT stabilisation energy correlates only weakly within the whole set of complexes.
KeywordsCCSD(T) DFT-SAPT Dispersion energy Electrostatic potential Halogen bond Noncovalent interactions σ-Hole σ-Hole magnitude σ-Hole size
This work was part of the Research Project RVO: 61388963 of the Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic. It was also supported by the Czech Science Foundation [P208/12/G016] and the operational program Research and Development for Innovations of the European Social Fund (CZ 1.05/2.1.00/03/0058). MHK acknowledges the kind support provided by the Alexander von Humboldt Foundation.
- 1.Hobza P, Müller Dethlef K (2009) Non-covalent interactions. Royal Society of Chemistry, CambridgeGoogle Scholar
- 9.Desiraju GR, Ho PS, Kloo L, Legon AC, Marguardt R, Metrangolo P, Politzer P, Resnati G, Rissanen K (2013) IUPAC definition of halogen bond. Pure Appl Chem 8:1711–1713Google Scholar
- 18.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, 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 Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, revision D.01. Gaussian, Inc., WallingfordGoogle Scholar
- 29.Werner H-J, Knowles PJ, Manby FR, Schuetz M, Celani P, Knizia G, Korona T, Lindh R, Mitrushenkov A, Rauhut G, Adler TB, Amos RD, Bernhardsson A, Berning A, Cooper DLO, Deegan MJ, Dobbyn AJ, Eckert F, Goll F, Hampel C, Hesselmann A, Hetzer G, Hrenar T, Jansen G, Koeppl C, Liu Y, Lloyd AW, Mata RA, May AJ, McNicholas SJ, Meyer W, Mura ME, Nicklass A, Palmieri P, Pflueger K, Pitzer K, Reiher M, Shiozaki T, Stoll H, Stone AJ, Tarroni R, Thorsteinsson T, Wang M, Wolf A (2010) MOLPRO, version 2010.1, a package of ab initio programs. See http://www.molpro.net
- 30.TURBOMOLE V6.3 2011, a development of the University of Karlsruhe and the Forschungszentrum Karlsruhe GmbH, 1989–2007, TURBOMOLE GmbH, since 2007; http://www.turbomole.com