Langmuir–Blodgett technique is utilized to deposit ultrathin films of Au38(SC2H4Ph)24 nanocluster onto solid surfaces such as mica and silicon. The morphologies of the films transferred at various surface pressures within the mono/bi/trilayer regime are studied by atomic force microscopy (AFM). The time spent on the water surface before the deposition has a decisive effect on the final ordering of nanoclusters within the network and is studied by fast AFM, X‐ray reflectivity, and grazing‐incidence wide‐angle X‐ray scattering.

A bidentate chiral dithiol (diBINAS) is utilised to bridge Au 25 nanoclusters to form oligomers. Separation by size allows the isolation of fractions that are stable thanks to the bidentate nature of the linker. The structure of the products is elucidated by smallangle X-ray scattering and calculated using density functional theory. Additional structural details are studied by diffusion-ordered nuclear magnetic resonance spectroscopy, transmission electron microscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. Significant changes in the optical properties are analysed by UV/Vis and fluorescence spectroscopies, with the latter demonstrating a strong emission enhancement. Furthermore, the emergent chiral characteristics are studied by circular dichroism. Due to the geometry constraints of the nanocluster assemblies, diBINAS can be regarded as a templating molecule, taking a step towards the directed selfassembly of metal clusters.

Recently the focus of the Langmuir–Blodgett technique as a method of choice to transfer monolayers from the air/water interface onto solid substrates in a controllable fashion has been shifting toward purely hydrophobic gold and silver nanoparticles. The fundamental interactions between particles that become relevant in the absence of polar groups range from dispersive attractions from the metal cores and repulsions between ligand shells to weaker entropic factors. The layer evolution is explored, starting with interfacial self-assembly upon solution spreading and domain and circular island formation, which subsequently merge into a complete monolayer and finally form multilayers or macroscopic wrinkles. Moreover, structural properties such as the core:ligand size ratio are investigated in the context of dispersive forces, whereby the nanoparticles with small cores and long ligands tend not to aggregate sufficiently to produce continuous films, those with large cores and short ligands were found to aggregate irreversibly, and those in between the two extremes were concluded to be able to form highly organized crystalline films. Similarly, the characteristics of the spreading solution such as the concentration and the solvent type crucially influence the film crystallinity, with the deciding factor being the degree of affinity between the capping ligand and the solvent used for spreading. Finally, the most common strategies employed to enhance the mechanical stability of the metal nanoparticle films along with the recent attempts to functionalize the particles in attempts to improve their applicability in the industry are summarized and evaluated in relation to their future prospects. One of the objectives of this feature article is to elucidate the differences between hydrophobic metal nanoparticles and typical amphiphilic molecules that the majority of the literature in the field describes and to familiarize the reader with the knowledge required to design Langmuir–Blodgett nanoparticle systems as well as the strategies to improve existing ones.

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We demonstrate a proof-of-concept of a new analytical technique to measure relative F atom exposure at the surfaces of fluorinated materials. The method is based on reactive-atom scattering (RAS) of Al atoms, produced by pulsed laser ablation of solid Al at 532 nm. The properties of the incident ground-state Al were characterized by laser-induced fluorescence (LIF); at typical ablation fluences, the speed distribution is approximately Maxwellian at ∼45000 K, with a most-probable kinetic energy of 187 kJ mol–1 and a mean of 560 kJ mol–1 When these Al atoms impact the surfaces of perfluorinated solids (poly­(tetrafluorethylene), PTFE) or liquids (perfluoropolyether, PFPE), gas-phase AlF products are clearly detectable by LIF on the AlF A–X band. Quantitative AlF yields were compared for a small representative set of a widely studied family of ionic liquids based on the common 1-alkyl-3-methylimidazolium ([C n mim]+) cation. Yields of (1.9 ± 0.2):1 were found from [C2mim]­[Tf2N] and [C8mim]­[Tf2N], containing the common fluorinated bis­(trifluoro­methylsulfonyl)­imide anion ([Tf2N]−). This is in quantitative agreement with previous independent low-energy ion scattering (LEIS) measurements and consistent with other independent results indicating that the longer cationic alkyl chains cover a larger fraction of the liquid surface and hence reduce anion exposure. The expected null result was obtained for the ionic liquid [C2mim]­[EtSO4] which contains no fluorine. These results open the way for further characterization and the potential application of this new variant of the RAS-LIF method.