Crystallization of molecular layers produced under confinement onto a surface

Jincheng Tong; Nathan de Bruyn; Adriana Alieva; Elizabeth J Legge; Matthew Boyes; Xiuju Song; Alvin J Walisinghe; Andrew J Pollard; Michael W Anderson; Thomas Vetter; Manuel Melle-Franco; Cinzia Casiraghi

doi:10.1038/s41467-024-45900-0

Crystallization of molecular layers produced under confinement onto a surface

Nat Commun. 2024 Mar 5;15(1):2015. doi: 10.1038/s41467-024-45900-0.

Authors

Affiliations

¹ Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK. tongjincheng@outlook.com.
² Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK.
³ National Physical Laboratory, Teddington, Middlesex, TW11 0LW, UK.
⁴ Advanced Technology Institute, University of Surrey, Guildford, Surrey, GU2 7XH, UK.
⁵ Curtin Institute for Computation, School for Molecular and Life Sciences, Curtin University, Perth, WA, 6845, Australia.
⁶ Department of Chemical Engineering and Analytical Sciences, University of Manchester, Manchester, M1 3AL, UK.
⁷ CICECO-Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro, 3810-193, Portugal.
⁸ Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK. cinzia.casiraghi@manchester.ac.uk.

Abstract

It is well known that molecules confined very close to a surface arrange into molecular layers. Because solid-liquid interfaces are ubiquitous in the chemical, biological and physical sciences, it is crucial to develop methods to easily access molecular layers and exploit their distinct properties by producing molecular layered crystals. Here we report a method based on crystallization in ultra-thin puddles enabled by gas blowing, which allows to produce molecular layered crystals with thickness down to the monolayer onto a surface, making them directly accessible for characterization and further processing. By selecting four molecules with different types of polymorphs, we observed exclusive crystallization of polymorphs with Van der Waals interlayer interactions, which have not been observed with traditional confinement methods. In conclusion, the gas blowing approach unveils the opportunity to perform materials chemistry under confinement onto a surface, enabling the formation of distinct crystals with selected polymorphism.