How does the composition of a PAH influence its microsolvation? A rotational spectroscopy study of the phenanthrene-water and phenanthridine-water clusters

Donatella Loru*, Amanda L. Steber, Pablo Pinacho, Sébastien Gruet, Berhane Temelso, Anouk M. Rijs, Cristóbal Pérez, Melanie Schnell

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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Abstract

We report on the noncovalent intermolecular interactions established between the polycyclic aromatic hydrocarbons phenanthrene and phenanthridine with water. Such noncovalent interactions involving extended aromatic systems and water molecules are ubiquitous in a variety of chemical and biological systems. Our study provides spectroscopic results on simple model systems to understand the impact that an extended aromatic surface and the presence of a heteroatom have on the nature of the noncovalent interactions established with the solvent. Microhydrated phenanthrene and phenanthridine clusters with up to three water molecules have been observed and unambiguously characterised by means of broadband rotational spectroscopy and quantum chemical calculations. The presence of a nitrogen atom in the backbone of phenanthridine remarkably affects the geometries of the water clusters and the interaction networks at play, with O-H⋯N and C-H⋯O interactions becoming preferred in the phenanthridine-water clusters over the O-H⋯π interactions seen in the phenanthrene-water clusters. The presence of this heteroatom induces nuclear quadrupole coupling, which was used to understand the cooperativity effects found with increasing cluster size. Our results provide important insight to draw a more complete picture of the noncovalent interactions involving solvent molecules and aromatic systems larger than benzene, and they can be significant to enhance our understanding of the aromatic-polar interactions at play in a myriad of chemical and biological contexts.

Original languageEnglish
Pages (from-to)9721-9732
Number of pages12
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number16
Early online date6 Apr 2021
DOIs
Publication statusPublished - 28 Apr 2021

Bibliographical note

Funding Information:
This work has been supported by the ERC Starting grant ‘Astrorot’ (grant agreement number 638027). D. L. and P. P. acknowledge the support of Alexander von Humboldt postdoctoral fellowships. A. M. R. acknowledges support via a Mildred-Dresselhaus guest professorship.

Publisher Copyright:
© the Owner Societies 2021.

Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.

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