期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 55, 期 5, 页码 1921-1924出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201508481
关键词
aromatic substitution; dispersion control; hydrogen bonds; molecular recognition; vibrational spectroscopy
资金
- Deutsche Forschungsgemeinschaft (DFG) in the priority program SPP 1807 on control of dispersion interactions [SU 121/5]
The supramolecular docking of methanol to anisole may occur via an OH center dot center dot center dot O hydrogen bond or via an OH center dot center dot center dot pi 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 pi coordination.
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