An N for Ir: The synthesis and X-ray crystal structure of a late-transition-metal complex with a terminal nitrido ligand and its hydrogenation to the related amido complex are reported (see scheme).

Lithium-coordinated polyaromatic anions such as tetrareduced corannulene, C(20)H(10)(4-) (1(4-)), are useful substrates to model and ultimately improve the graphitic electrodes in lithium-ion (Li(+)) batteries. Previous studies suggested that 1(4-) forms dimers encasing four Li(+) ions in solution. Here, we report a single-crystal x-ray diffraction analysis confirming the formation of a sandwich-type supramolecular aggregate with a high degree of alkali metal intercalation. In contrast to the prior model, our data reveal that five Li(+) ions are sandwiched between the two tetrareduced corannulene decks, and (7)Li nuclear magnetic resonance spectroscopy delineates a conserved structure in tetrahydrofuran solution. Remarkably, the sandwich is robust in both solution and solid states even in the presence of crown ethers that compete for Li(+) coordination. These results should help elucidate Li(+) intercalation motifs between curved carbon surfaces more broadly.

Nanoscale localization of electromagnetic fields using metallic nanostructures can catalyze chemical reactions in their immediate vicinity. Local optical field confinement and enhancement is also exploited to attain single-molecule detection sensitivity in surface-and tip-enhanced Raman (TER) spectroscopy. In this work, we observe and investigate the sporadic formation of 4-nitrobenzenethiolate upon TER imaging of a 4-nitrobenzenethiol (4NBT) monolayer on Au(111). Density functional theory (DFT), finite-difference timedomain (FDTD), and finite element method (FEM) calculations together confirm that this chemical reaction does not occur as a result of thermal desorption of the molecule, which requires temperatures in excess of 2100 K at the tip−sample junction. Our combined experimental and theoretical analyses strongly suggest that the chemical transformations observed throughout the course of TERS mapping is not driven by plasmonic photothermal heating, but rather by plasmon-induced hot carriers.

Trap for electrophiles: The reaction of corannulene with halogenated hydrocarbons in the presence of AlCl3 gave the products of an electrophilic attack on the hub carbon atom of the curved aromatic surface (see picture). The X‐ray diffraction characterization of a series of bowl‐shaped cations illustrates structural deformations caused by the site‐directed interior surface functionalization.

The ion size matters: the structures of corannulene monoanions crystallized with Cs(+) and Rb(+) ions in the presence of [18]crown-6 reveal the intrinsic binding preferences of alkali metals and allow evaluation of the bowl deformation caused by negative charge distribution and metal binding. The large cesium cation coordinates exclusively to the concave face of C(20) H(10)(-), whereas the smaller rubidium cation exhibits convex binding.