Three-Component Gold(I)-Catalyzed Alkoxyvinylation.

Acetylene has been underexploited despite being a highly valuable feedstock for chemical synthesis. We have developed the first true gold(I)-catalyzed intermolecular three-component reaction between acetylene, alkenes, and alcohols to afford ß-vinyl hemiaminal scaffolds from N-vinyl amides. Unusual biscyclopropyl and 3-vinyl N-heterocyclic scaffolds were obtained through the incorporation of a second N-vinyl unit or tethered alkene into the starting material.

The Journey for the Synthesis of Large Acenes.

Acenes, the group of polycyclic aromatic hydrocarbons (PAHs) with linearly fused benzene rings, possess distinctive electronic properties with potential applicability in material science. Hexacene was the largest acene obtained and characterized in the last century, followed by heptacene in 2006. Since then, a race for obtaining the largest acene resulted in the development of several members of this family as well as diverse innovative synthetic strategies, from solid-state chemistry to the promising on-surface chemistry. This last technique allows the obtention of higher acenes, up to tridecacene, the largest acene so far. This review presents the different methodologies employed for the synthesis of acenes, highlighting the newest studies, to provide a much more thorough understanding of the essence of the electronic structure of this captivating group of organic compounds.

On-Surface Synthesis and Determination of the Open-Shell Singlet Ground State of Tridecacene.

The character of the electronic structure of acenes has been the subject of longstanding discussion. However, convincing experimental evidence of their open-shell character has so far been missing. Here, we present the on-surface synthesis of tridecacene molecules by thermal annealing of octahydrotridecacene on a Au(111) surface. We characterized the electronic structure of the tridecacene by scanning probe microscopy, which reveals the presence of an inelastic signal at 126 meV. We attribute the inelastic signal to spin excitation from the singlet diradical ground state to the triplet excited state. To rationalize the experimental findings, we carried out many-body ab initio calculations as well as model Hamiltonians to take into account the effect of the metallic substrate. Moreover, we provide a detailed analysis of how the dynamic electron correlation and virtual charge fluctuation between the molecule and metallic surface reduces the singlet-triplet band gap. Thus, this work provides the first experimental confirmation of the magnetic character of tridecacene.

On surface synthesis of an eleven-ring sulfur-doped nonacene.

Dithienoacenes with a heptacene core, heptaceno[2,3-b:11,12-b']bis[1]benzothiophene, have been synthesized through the combination of solution and surface assisted chemistry. The atomic composition, structural arrangement and electronic properties of the molecules on the Au(111) surface have been deeply explored by non-contact atomic force microscopy (nc-AFM), bond-resolved scanning tunnelling microscopy (BR-STM) and scanning tunneling spectroscopy (STS) corroborated by density functional theory (DFT) calculations. Our combined experiments reveal modifications induced by sulfur substitution.