RESUMEN
On-surface synthesis has become a prominent method for growing low-dimensional carbon-based nanomaterials on metal surfaces. However, the necessity of decoupling organic nanostructures from metal substrates to exploit their properties requires either transfer methods or new strategies to perform reactions directly on inert surfaces. The use of on-surface light-induced reactions directly on semiconductor/insulating surfaces represents an alternative approach to address these challenges. Here, exploring the photochemical activity of different organic molecules on a SnSe semiconductor surface under ultra-high vacuum, we present a novel on-surface light-induced reaction. The selective photodissociation of the anhydride group is observed, releasing CO and CO2. Moreover, we rationalize the relationship between the photochemical activity and the π-conjugation of the molecular core. The different experimental behaviour of two model anhydrides was elucidated by theoretical calculations, showing how the molecular structure influences the distribution of the excited states. Our findings open new pathways for on-surface synthesis directly on technologically relevant substrates.
RESUMEN
The design of supramolecular organic radical cages and frameworks is one of the main challenges in supramolecular chemistry. Their interesting material properties and wide applications make them very promising for (photo)redox catalysis, sensors, or host-guest spin-spin interactions. However, the high reactivity of radical organic systems makes the design of such supramolecular radical assemblies challenging. Here, we report the on-surface synthesis of a purely organic supramolecular radical framework on Au(111), by combining supramolecular and on-surface chemistry. We employ a tripodal precursor, functionalized with 7-azaindole groups that, catalyzed by a single gold atom on the surface, forms a radical molecular product constituted by a π-extended fluoradene-based radical core. The radical products self-assemble through hydrogen bonding, leading to extended 2D domains ordered in a Kagome-honeycomb lattice. This approach demonstrates the potential of on-surface synthesis for developing 2D supramolecular radical organic chemistry.
RESUMEN
Two-dimensional (2D) layered group IV-VI semiconductors attract great interest due to their potential applications in nanoelectronics. Depending on the dimensionality, different phases of the same material can present completely different electronic and optical properties, expanding its applications. Here, we present a combined experimental and theoretical study of the atomic structure and electronic properties of epitaxial SnSe structures grown on a metallic Au(111) substrate, forming almost defect-free 2D layers. We describe a coverage-dependent transition from a metallicß-SnSe to a semiconductingα-SnSe phase. The combination of scanning tunneling microscopy/spectroscopy, non-contact atomic force microscopy, x-ray photoelectron spectroscopy/diffraction and angle-resolved photoemission spectroscopy, complemented by density functional theory, provides a comprehensive study of the geometric and electronic structure of both phases. Our work demonstrates the possibility to grow two distinct SnSe phases on Au(111) with high quality and on a large scale. The strong interaction with the substrate allows the stabilization of the previously experimentally unreportedß-SnSe, while the ultra-thin films of orthorhombicα-SnSe are structurally and electronically equivalent to bulk SnSe.
RESUMEN
One-dimensional (1D) metal-organic (MO) nanowires are captivating from fundamental and technological perspectives due to their distinctive magnetic and electronic properties. The solvent-free synthesis of such nanomaterials on catalytic surfaces provides a unique approach for fabricating low-dimensional single-layer materials with atomic precision and low amount of defects. A detailed understanding of the electronic structure of MO polymers such as band gap and dispersive bands is critical for their prospective implementation into nanodevices such as spin sensors or field-effect transistors. Here, we have performed the on-surface reaction of quinoidal ligands with single cobalt atoms (Co-QDI) on a vicinal Au(788) surface in ultra-high vacuum. This procedure promotes the growth and uniaxial alignment of Co-QDI MO chains along the surface atomic steps, while permitting the mapping of their electronic properties with space-averaging angle-resolved photoemission spectroscopy. In the direction parallel to the principal chain axis, a well-defined 1D band structure with weakly dispersive and dispersive bands is observed, confirming a pronounced electron delocalization. Low-temperature scanning tunneling microscopy/spectroscopy delves into the atomically precise structure of the nanowires and elucidates their narrow bandgap. These findings are supported with GW0 band structure calculations showing that the observed electronic bands emanate from the efficient hybridization of Co(3d) and molecular orbitals. Our work paves the way towards a systematic search of similar 1D π-d hybridized MO chains with tunable electronic and magnetic properties defined by the transition or rare earth metal atom of choice.
