Diamondoid ether clusters in helium nanodroplets

Abstract

Diamondoid ethers were introduced into superfluid helium nanodroplets and the resulting clusters were analyzed by time-of-flight mass spectrometry. Clusters of higher abundances (magic number clusters) were identified and the corresponding...

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

“…In previous studies of self-organized HND aggregates consisting of diamondoid molecules such as adamantane, [20][21][22] diamantane 23 and diamondoid ethers, 24 certain preferences for cluster abundances were found that belonged to particularly stable geometries. These observed privileged abundances were termed as magic numbers.…”

“…S3, ESI†). Building on our previous benchmarking for similar systems, 23,24 we performed a search for viable cluster structures using CREST based on the GFN methods, 36,37 more specifically, by applying the iterative meta -dynamic sampling for non-covalently bound systems (NCI-iMTD mode). After identifying the best candidates, we performed single point computations on these geometries using the B3LYP-gCP-D3(BJ)-ABC/def2-TZVPP level of theory.…”

“…The choice of the DFT method was based on our previous benchmarking of similarly bulky molecules in the HNDs. 23,24 We found that using the D3(BJ) dispersion correction, 34,35,38 the three-body dispersion contribution term implemented in Orca as well as the geometrical counterpoise (gCP) correction 39 successfully accounts for subtle intermolecular interactions and mitigates the basis-set superposition errors (BSSEs), respectively. Please see the ESI † for more computational details.…”

“…This clearly demonstrates that not only does the hydrogen bonding region expectedly push out all He out of its reach of influence, but also that diamondoid cages themselves preferentially engage in the intermolecular dispersion interaction rather than in simple ''solvation'' with helium, in line with our previous findings. 23,24 Concerning the number of water molecules observed for acid clusters, smaller assemblies of 1a and 2a do not favor the presence of water and when increasing the cluster size one observes the incorporation of a single water molecule (Fig. S1, ESI †).…”

“…28 We previously investigated the influence of dispersion interactions on the self-assembly of less-polar diamondoids in HNDs. 23,24 Going one step further, in the scope of this study we have now studied cluster formation of diamondoid acids 1a-4a and alcohols 1b-4b (Fig. 1) under HND conditions.…”