Kumar, S., Singh, S.K., Vaishnav, J.K. et al. (2 more authors) (2017) Interplay among electrostatic, dispersion and steric interactions: Spectroscopy and quantum chemical calculations of π-hydrogen bonded complexes. ChemPhysChem, 18 (7). pp. 828-838. ISSN 1439-71439
Abstract
π-hydrogen bonding interactions are ubiquitous in both materials and biology. Despite their relatively weak nature great progress has been made in their investigation by experimental and theoretical methods, but this becomes significantly more complicated when secondary intermolecular interactions are present. In this study the effect of successive methyl substitution on the supramolecular structure and interaction energy of indole⋯methylated benzene (ind⋯n-mb, n = 1–6) complexes is probed through a combination of supersonic jet experiment and benchmark quality quantum chemical calculations. It is demonstrated that additional secondary interactions introduce a subtle interplay among electrostatic and dispersion forces, as well as steric repulsion, which fine-tunes the overall structural motif. Resonant Two-Photon Ionization (R2PI) and IR-UV double resonance spectroscopy techniques were used to probe jet-cooled ind⋯n-mb (n = 2, 3, 6) complexes, with red-shifting of the N–H IR stretching frequency showing that increasing the degree of methyl substitution increases the strength of the primary N–H⋯π interaction. Ab initio harmonic frequency and binding energy calculations confirm this trend for all six complexes. Electronic spectra of the three dimers are broad and structureless, with quantum chemical calculations revealing that this is likely due to multiple tilted conformations of each dimer possessing similar stabilization energies.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2017 Wiley. This is an author produced version of a paper subsequently published in ChemPhysChem. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 02 Feb 2017 15:37 |
Last Modified: | 26 Jan 2018 01:38 |
Published Version: | https://doi.org/10.1002/cphc.201601405 |
Status: | Published |
Publisher: | Wiley: 12 months |
Refereed: | Yes |
Identification Number: | 10.1002/cphc.201601405 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:111278 |