From One-Dimensional Disordered Racemate to Ordered Racemic Conglomerates through Metal-Coordination-Driven Self-Assembly at the Liquid-Solid Interface

Tianze Hu; Andrea Minoia; Gangamallaiah Velpula; Kanykei Ryskulova; Kristof Van Hecke; Roberto Lazzaroni; Kunal S Mali; Richard Hoogenboom; Steven De Feyter

doi:10.1002/chem.202302545

From One-Dimensional Disordered Racemate to Ordered Racemic Conglomerates through Metal-Coordination-Driven Self-Assembly at the Liquid-Solid Interface

Chemistry. 2024 Jan 8;30(2):e202302545. doi: 10.1002/chem.202302545. Epub 2023 Nov 15.

Authors

Tianze Hu¹, Andrea Minoia², Gangamallaiah Velpula¹, Kanykei Ryskulova³, Kristof Van Hecke⁴, Roberto Lazzaroni², Kunal S Mali¹, Richard Hoogenboom³, Steven De Feyter¹

Affiliations

¹ KU Leuven, Division of Molecular Imaging and Photonics, Department of Chemistry, Celestijnenlaan 200F, 3001, Leuven, Belgium.
² Laboratory for Chemistry of Novel Materials, Materials Research Institute, University of Mons, Place du Parc 20, 7000, Mons, Belgium.
³ Supramolecular Chemistry Group, Centre of Macromolecular Chemistry, Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4, 9000, Ghent, Belgium.
⁴ XStruct, Department of Chemistry, Ghent University, Krijgslaan 281 S3, 9000, Ghent, Belgium.

PMID: 37840008
DOI: 10.1002/chem.202302545

Abstract

In recent years, there has been significant focus on investigating and controlling chiral self-assembly, specifically in the context of enantiomeric separation. This study explores the self-assembly behavior of 4-dodecyl-3,6-di(2-pyridyl)pyridazine (DPP-C12) at the interface between heptanoic acid (HA) and highly oriented pyrolytic graphite (HOPG) using a combination of scanning tunneling microscopy (STM) and multiscale molecular modeling. The self-assembled monolayer structure formed by DPP-C12 is periodic in one direction, but aperiodic in the direction orthogonal to it. These structures resemble 1D disordered racemic compounds. Upon introducing palladium [Pd(II)] ions, complexing with DPP-C12, these 1D disordered racemic compounds spontaneously transform into 2D racemic conglomerates, which is rationalized with the assistance of force-field simulations. Our findings provide insights into the regulation of two-dimensional chirality.

Keywords: conglomerates; coordination interactions; multiscale molecular modeling; scanning tunneling microscopy; self-assembly.

Abstract

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