Federico Masini

Direct observation of molecular preorganization for chirality transfer on a catalyst surface.

Scanning tunneling microscopy and theoretical calculations shed light on an asymmetric heterogeneous catalyst. The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that continued progress in the area is uncertain. We show that the investigation of heterogeneous asymmetric induction with single-site resolution sufficient to distinguish stereochemical conformations at the submolecular level is finally accessible. A combination of scanning tunneling microscopy and density functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different submolecular binding sites on the modifier at the reaction temperature.

Chiral Induction by Seeding Surface Assemblies of Chiral Switches

It is demonstrated by scanning tunneling microscopy that coadsorption of a molecular chiral switch with a complementary, intrinsically chiral induction seed on the Au(111) surface leads to the formation of globally homochiral molecular assemblies.

A Surface Coordination Network Based on Copper Adatom Trimers

Surface coordination networks formed by co-adsorption of metal atoms and organic ligands have interesting properties, for example regarding catalysis and data storage. Surface coordination networks studied to date have typically been based on single metal atom centers. The formation of a novel surface coordination network is now demonstrated that is based on network nodes in the form of clusters consisting of three Cu adatoms. The network forms by deposition of tetrahydroxybenzene (THB) on Cu(111) under UHV conditions. As shown from a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations, all four hydroxy groups of THB dehydrogenate upon thermal activation at 440 K. This highly reactive ligand binds to Cu adatom trimers, which are resolved by high-resolution STM. The network creates an ordered array of mono-dispersed metal clusters constituting a two-dimensional analogue of metal-organic frameworks.

Stereodirection of an α-Ketoester at Sub-molecular Sites on Chirally Modified Pt(111): Heterogeneous Asymmetric Catalysis

Chirally modified Pt catalysts are used in the heterogeneous asymmetric hydrogenation of α-ketoesters. Stereoinduction is believed to occur through the formation of chemisorbed modifier-substrate complexes. In this study, the formation of diastereomeric complexes by coadsorbed methyl 3,3,3-trifluoropyruvate, MTFP, and (R)-(+)-1-(1-naphthyl)ethylamine, (R)-NEA, on Pt(111) was studied using scanning tunneling microscopy and density functional theory methods. Individual complexes were imaged with sub-molecular resolution at 260 K and at room temperature. The calculations find that the most stable complex isolated in room-temperature experiments is formed by the minority rotamer of (R)-NEA and pro-S MTFP. The stereodirecting forces in this complex are identified as a combination of site-specific chemisorption of MTFP and multiple non-covalent attractive interactions between the carbonyl groups of MTFP and the amine and aromatic groups of (R)-NEA.

Formation of trioctylamine from octylamine on Au(111)

The adsorption of octylamine on Au(111) under ultrahigh vacuum conditions is investigated. The molecules surprisingly undergo a thermally activated chemical reaction, resulting in formation of trioctylamine as confirmed both by X-ray photoelectron spectroscopy (XPS) and by comparison to the scanning tunneling microscopy (STM) signature of trioctylamine deposited directly onto the surface.

Controlling Chiral Organization of Molecular Rods on Au(111) by Molecular Design

Chiral self-assembled structures formed from organic molecules adsorbed on surfaces have been the subject of intense investigation in the recent decade, owing both to relevance in applications such as enantiospecific heterogeneous catalysis or chiral separation as well as to fundamental interest, for example, in relation to the origin of biomolecular homochirality. A central target is rational design of molecular building blocks allowing transfer of chirality from the molecular to the supramolecular level. We previously studied the surface self-assembly of a class of linear compounds based on an oligo(phenylene ethynylene) backbone, which were shown to form a characteristic windmill adsorption pattern on the Au(111) surface. However, since these prochiral compounds were intrinsically achiral, domains with oppositely oriented windmill motifs and related conformational surface enantiomers were always realized in equal proportion. Here we report on the enantioselective, high yield chemical synthesis of a structurally related but intrinsically chiral compound in which two peripheral tert-butyl substituents are replaced by sec-butyl groups, each containing an (S) chiral center. Using scanning tunneling microscopy under ultrahigh vacuum conditions, we characterize the adsorption structures formed from this compound on the Au(111) surface. The perturbation introduced by the modified molecular design is found to be sufficiently small so structures form that are closely analogous to those observed for the original tert-butyl substituted compound. However, as demonstrated from careful statistical analysis of high-resolution STM images, the introduction of the two chiral (S)-sec-butyl substituents leads to a strong preference for windmill motifs with one orientation, demonstrating control of the chiral organization of the molecular backbones through rational molecular design.

From zero to two dimensions: supramolecular nanostructures formed from perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) and Ni on the Au(111) surface through the interplay between hydrogen-bonding and electrostatic metal-organic interactions

AbstractSupramolecular self-assembly of the organic semiconductor perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) together with Ni atoms on the inert Au(111) surface has been investigated using high-resolution scanning tunneling microscopy under ultrahigh vacuum conditions. We demonstrate that it is possible by tuning the co-adsorption conditions to synthesize three distinct self-assembled Ni-PTCDI nanostructures from zero-dimensional (0-D) nanodots over one-dimensional (1-D) chains to a two-dimensional (2-D) porous network. The subtle interplay among non-covalent interactions responsible for the formation of the observed structures has been revealed from force-field structural modeling and calculations of partial charges, bond orders and binding energies in the structures. A unifying motif for the 1-D chains and the 2-D network is found to be double N-H…O hydrogen bonds between PTCDI molecules, similar to the situation found in surface structures formed from pure PTCDI. Most interestingly, we find that the role of the Ni atoms in forming the observed structures is not to participate in metal-organic coordination bonding. Rather, the Ni adatoms acquire a negative partial charge through interaction with the substrate and the Ni-PTCDI interaction is entirely electrostatic.

Scanning Tunneling Microscopy Measurements of the Full Cycle of a Heterogeneous Asymmetric Hydrogenation Reaction on Chirally Modified Pt(111)

The hydrogenation of a prochiral substrate, 2,2,2-trifluoroacetophenone (TFAP), on Pt(111) was studied using room-temperature scanning tunneling microscopy (STM) measurements. The experiments were carried out both on a clean surface and on a chirally modified surface, using chemisorbed (R)-(+)-1-(1-naphthyl)ethylamine, ((R)-NEA), as the modifier. On the nonmodified surface, introduction of H2 at a background pressure of ∼1 × 10(-6) mbar leads to the rapid break-up of TFAP dimer structures followed by the gradual removal of all TFAP-related images. During the latter step, some monomers display an extra protrusion compared to TFAP in dimer structures. They are attributed to a half-hydrogenated intermediate. The introduction of H2 to a mixture of (R)-NEA and TFAP on Pt(111) leads to the removal of TFAP without any change in the population of the modifier, as required for an efficient chirally modified catalyst.