Kinked row-induced chirality driven by molecule-substrate interactions.

Combining STM measurements on three different substrates (HOPG, MoS2, and Au[111]) together with DFT calculations allow for analysis of the origin of the self-assembly of 4-cyano-4'-n-decylbiphenyl (10CB) molecules into kinked row structures using a previously developed phenomenological model. This molecule has an alkyl chain with 10 carbons and a cyanobiphenyl group with a particularly large dipole moment. 10CB represents a toy model that we use here to unravel the relationship between the induced kinked structure, in particular the corresponding chirality expression, and the balanced intermolecular/molecule-substrate interaction. We show that the local ordered structure is driven by the typical alkyl chain/substrate interaction for HOPG and Au[111] and the cyanobiphenyl group/substrate interaction for MoS2. The strongest molecule/substrate interactions are observed for MoS2 and Au[111]. These strong interactions should have led to non-kinked, commensurate adsorbed structures. However, this latter appears impossible due to steric interactions between the neighboring cyanobiphenyl groups that lead to a fan-shape structure of the cyanobiphenyl packing on the three substrates. As a result, the kink-induced chirality is particularly large on MoS2 and Au[111]. A further breaking of symmetry is observed on Au[111] due to an asymmetry of the facing molecules in the rows induced by similar interactions with the substrate of both the alkyl chain and the cyanobiphenyl group. We calculate that the overall 10CB/Au[111] interaction is of the order of 2 eV per molecule. The close 10CB/MoS2 interaction, in contrast, is dominated by the cyanobiphenyl group, being particularly large possibly due to dipole-dipole interactions between the cyanobiphenyl groups and the MoS2 substrate.

Switching at the nanoscale: light- and STM-tip-induced switch of a thiolated diarylethene self-assembly on Au(111).

The light-induced and STM-tip-induced switching of photochromic thiol functionalized terphenylthiazole-based diarylethene self-assembly on Au(111) has been investigated in ambient conditions. For such a purpose, we took advantage of the formation of highly ordered domains of opened-ring (1o) or closed-ring (1c) diarylethene isomers. We evidenced a STM-tip-induced switching for the 1o isomer characterized by a tip bias threshold of 1000 mV above which switching of all molecules of the ordered 1o domains occurs into the 1c isomer. In contrast, switching from 1c form into 1o form is not observed at the same tunnelling conditions within a domain formed by ordered 1c molecules. We compared tip-induced switching of ordered 1o domains and switching of single 1o isomers embedded in 1c domains. This led to the demonstration that the process of switching of the 1o isomer is determined by geometry of the molecules but also that the stability of the switched 1c isomer depends on the nature of the surrounding isomers. We also compare tip-induced switching and switching under the action of external UV light irradiation of ordered 1o domains. In contrast with STM tip-induced switching, the UV light induces switching of 1o domains into their stable 1c form, in agreement with a collective switching under irradiation, which cannot occur under the action of STM tip.

Nonuniform STM Contrast of Self-Assembled Tri-n-octyl-triazatriangulenium Tetrafluoroborate on HOPG.

We have assembled 4,8,12-tri-n-octyl-4,8,12-triazatrianguleniumtetrafluoroborate (TATA-BF4) on highly oriented pyrolytic graphite (HOPG) and have studied the structure and tunneling properties of this self-assembled monolayer (SAM) using scanning tunneling microscopy (STM) under ambient conditions. We show that the triazatriangulenium cations TATA+ form hexagonally packed structures driven by the interaction between the aromatic core and the HOPG lattice, as evidenced by density functional theory (DFT) modeling. According to the DFT results, the three alkyl chains of the platform tend to follow the main crystallographic directions of HOPG, leading to a different STM appearance. The STM contrast of the SAM shows that the monolayer is formed by two types of species, namely, TATA+ with BF4- counterions on top and without them. The cationic TATA+ platform gives rise to a seemingly higher appearance than neutral TATA-BF4, in contrast to observations made on metallic substrates. The variation of the STM tunneling parameters does not change the relative difference of contrast, revealing the stability of both species on HOPG. DFT calculations show that TATA-BF4 on HOPG has sufficient binding energy to resist dissociation into TATA+ and BF4-, which might occur under the action of the electric field in the tunneling gap during STM scanning.

Gold Nanoparticle Self-Aggregation on Surface with 1,6-Hexanedithiol Functionalization.

Here we study the morphology and the optical properties of assemblies made of small (17 nm) gold nanoparticles (AuNPs) directly on silicon wafers coated with (3-aminopropyl)trimethoxysilane (APTES). We employed aliphatic 1,6-hexanedithiol (HDT) molecules to cross-link AuNPs during a two-stage precipitation procedure. The first immersion of the wafer in AuNP colloidal solution led mainly to the attachment of single particles with few inclusions of dimers and small aggregates. After the functionalization of precipitated NPs with HDT and after the second immersion in the colloidal solution of AuNP, we detected a sharp rise in the number of aggregates compared to single AuNPs and their dimers. The lateral size of the aggregates was about 100 nm, while some of them were larger than 1µm. We propose that the uncompensated dipole moment of the small aggregates appeared after the first precipitation and acts further as the driving force accelerating their further growth on the surface during the second precipitation. By having such inhomogeneous surface coating, the X-ray reciprocal space maps and modulation polarimetry showed well-distinguished signals from the single AuNPs and their dimers. From these observations, we concluded that the contribution from aggregated AuNPs does not hamper the detection and investigation of plasmonic effects for AuNP dimers. Meantime, using unpolarized and polarized light spectroscopy, the difference in the optical signals between the dimers, being formed because of self-aggregation and the one being cross-linked by means of HDT, was not detected.