title: Control over the Hydrogen-Bond Docking Site in Anisole by Ring Methylation.
abstract: The supramolecular docking of methanol to anisole may occur via an OH⋅⋅⋅O hydrogen bond or via an OH⋅⋅⋅π contact. The subtle balance between these two structures can be varied in supersonic jets by one order of magnitude through single to triple methylation of the aromatic ring and introduction of a single tert-butyl substituent, as evidenced by infrared spectroscopy. This steep variation makes it possible to assess the accuracy of relative quantum-chemical energy predictions on a kJ mol(-1) level, promising insights into inductive, mesomeric, and dispersive effects. The zero-point-corrected B3LYP-D3/aVTZ level is shown to provide an accurate relative description of the two very different hydrogen bonds, similar to a wavefunction-based protocol including CCSD(T) corrections applied to the same structures. M06-2X alone systematically overestimates the stability of π coordination.
authors.affiliation: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, 37077, Göttingen, Deutschland.
authors.forename: Hannes C
authors.identifier: http://orcid.org/0000-0003-4343-9542
authors.initials: HC
authors.lastname: Gottschalk
authors.affiliation: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, 37077, Göttingen, Deutschland.
authors.forename: Jonas
authors.identifier: http://orcid.org/0000-0001-5214-4936
authors.initials: J
authors.lastname: Altnöder
authors.affiliation: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, 37077, Göttingen, Deutschland.
authors.forename: Matthias
authors.identifier: http://orcid.org/0000-0002-8561-6423
authors.initials: M
authors.lastname: Heger
authors.affiliation: Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, 37077, Göttingen, Deutschland. msuhm@gwdg.de.
authors.forename: Martin A
authors.identifier: http://orcid.org/0000-0001-8841-7705
authors.initials: MA
authors.lastname: Suhm
keywords: aromatic substitution; dispersion control; hydrogen bonds; molecular recognition; vibrational spectroscopy