Wetting vs Droplet Aggregation: A Broadband Rotational Spectroscopic Study of 3‐Methylcatechol⋅⋅⋅Water Clusters

• Published in: Angewandte Chemie 2023-10, Vol.135 (44)
• Main Authors: Hazrah, Arsh S., Insausti, Aran, Ma, Jiarui, Al‐Jabiri, Mohamad H., Jäger, Wolfgang, Xu, Yunjie
• Format: Article
• Language: English
• Subjects: Broadband; Chemistry; Computational chemistry; Droplets; Hydrates; Rotational spectra; Solvation; Spectroscopy; Water chemistry; Wetting
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202310610

Two competing solvation pathways of 3‐methylcatechol (MC), an atmospherically relevant aromatic molecule, with up to five water molecules were explored in detail by using a combination of broadband rotational spectroscopy and computational chemistry. Theoretically, two different pathways of solvation emerge: the commonly observed droplet pathway which involves preferential binding among the water molecules while the solute serves as an anchor point for the formation of a water cluster, and an unexpected wetting pathway which involves interactions between the water molecules and the aromatic face of MC, i.e., a wetting of the π‐surface. Conclusive identification of the MC hydrate structures, and therefore the wetting pathway, was facilitated by rotational spectra of the parent MC hydrates and several H 2 18 O and 13 C isotopologues which exhibit splittings associated with methyl internal rotation and/or water tunneling motions. Theoretical modelling and analyses offer insights into the tunneling and conversion barriers associated with the observed hydrate conformers and the nature of the non‐covalent interactions involved in choosing the unusual wetting pathway.