title: Interplay among Electrostatic, Dispersion, and Steric Interactions: Spectroscopy and Quantum Chemical Calculations of π-Hydrogen Bonded Complexes.
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 experiments 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 and IR-UV double-resonance spectroscopy techniques are used to probe jet-cooled ind⋅⋅⋅n-mb (n=2, 3, 6) complexes, with redshifting 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 to be due to multiple tilted conformations of each dimer possessing similar stabilization energies.
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune, 411008, Maharashtra, India.|Present address: Department of Dynamics at Surfaces, Max Planck Institute of Biophysical Chemistry, Am Faßberg 11, 37077, Gottingen, Germany.
authors.forename: Sumit
authors.initials: S
authors.lastname: Kumar
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune, 411008, Maharashtra, India.
authors.forename: Santosh K
authors.initials: SK
authors.lastname: Singh
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune, 411008, Maharashtra, India.|Present address: Indian Institute of Technology (IIT) Indore, Khandwa Rd, Simrol, Madhya, Pradesh, 452020, India.
authors.forename: Jamuna K
authors.initials: JK
authors.lastname: Vaishnav
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.
authors.forename: J Grant
authors.initials: JG
authors.lastname: Hill
authors.affiliation: Department of Chemistry, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune, 411008, Maharashtra, India.
authors.forename: Aloke
authors.initials: A
authors.lastname: Das
mesh_terms: D001554:Benzene / Q000737:chemistry*; D006860:Hydrogen Bonding; D046911:Macromolecular Substances / Q000737:chemistry; D013058:Mass Spectrometry; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D055672:Static Electricity
chemical_list: D046911:Macromolecular Substances; D001554:Benzene
keywords: ab initio calculations; electronic spectroscopy; laser spectroscopy; noncovalent interactions; vibrational spectroscopy