Title: Nanostructured supramolecular networks from self-assembled diamondoid molecules under ultracold conditions

Authors: Marija Alešković, Florian Küstner, Roman Messner, Florian Lackner, Wolfgang E. Ernst, Marina Šekutor

DOI: https://doi.org/10.1039/D3CP02367B

Date: 06/13/2023

Working Group: WG4

Grant Period: GAPG-5/WG4

Grant Period Goal (number): [GAPG-2/WG1], [GAPG-3/WG2], [GAPG-5/WG4]

Delivered computational code associated wih the publication (name): Orca 5.0.3 program package using the B3LYP-gCP-D3(BJ)-ABC/def2-TZVPP level of theory

Covered deliverables from the MoU (number): 1.2.1, 2.4.2, 4.3.2

Countries involved: Croatia, Austria

Number of female/young/ITC coauthors: 2

Abstract: Diamondoid molecules and their derivatives have attracted attention as fascinating building blocks for advanced functional materials. Depending on the balance between hydrogen bonds and London dispersion interactions, they can self-organize in different cluster structures with functional groups tailored for various applications. Here, we present a new approach to supramolecular aggregation where self-assembly of diamondoid acids and alcohols in the ultracold environment of superfluid helium nanodroplets (HNDs) was analyzed by a combination of time-of-flight mass spectrometry and computational tools. Experimentally observed magic numbers of the assembled cluster sizes were successfully identified and computed cluster structures gave valuable insights into a different conglomeration mode when compared to previously explored less-polar diamondoid derivatives. We have confirmed that functional groups acting as good hydrogen bond donors completely take over the self-organization process, resulting in fascinating pair-wise or cyclic supramolecular assemblies. Particularly noteworthy is that mono- and bis-substituted diamondoid derivatives of both series engage in completely different modes of action, which is reflected in differing non-covalent cluster geometries. Additionally, formed cyclic clusters with a polar cavity in the center and a non-polar diamondoid outer layer can be of high interest in porous material design and provide insights into the structural requirements needed to produce bulk materials with desired properties.


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