Hydrogen peroxide production by direct synthesis (H 2 + O 2 → H 2 O 2 ) is a promising alternative to the commercialized indirect process involving sequential hydrogenation and oxidation of anthraquinones. Metal dopants are known to enhance the performance of Pd-based catalysts in this reaction by increasing H 2 O 2 rates and selectivity. Recently, binary and ternary Pd-based alloys with Pb have been proposed as catalysts by theoretical studies, but these compositions lack experimental proof. Herein, shape-selective Pd 3 Pb nanocrystals were created to produce catalysts where the active and doping metal are colocalized to a fine extent. This strategy enables us to study the effects of both Pb doping and nanocrystal shape on the catalytic performance in direct H 2 O 2 synthesis. In order to achieve these goals, we developed a procedure for the shape-controlled synthesis of Pb-doped nanocrystals with phase-pure, intermetallic Pd 3 Pb composition. By a change of the ligands, uniform Pd 3 Pb nanocrystals with cubic, cuboctahedral, and spherical shapes as well as flowerlike aggregates were obtained, which were supported on acid-treated TiO 2 . We show that the catalytic efficiency in direct H 2 O 2 synthesis not only is influenced by the nanocrystal composition but also depends on the particle shape. Pd 3 Pb cubes, predominately terminated by their (200) facets, outperformed not only the monometallic Pd reference catalyst but also Pd 3 Pb nanocrystals with other shapes. Further DFT calculations and surface studies indicated not only the electronic modification of Pd surface atoms with a higher barrier for O 2 dissociation on Pd 3 Pb but also a lack of larger Pd ensembles in Pd 3 Pb cubes which are known to cleave O−O bonds and form water.

Different external stimuli can affect the molecular structure of molecular gold strings, influencing their physical properties.

Orthogonal ligand scaffolds, consisting of soft and hard donor sites, are useful tools for the selective synthesis of heteronuclear coinage metal compounds, controlling their coordination geometry and tuning their photophysical properties.

A coumarin functionalized aminodiphosphine has been introduced as a bidentate ligand in coinage metal chemistry. Mono-, di-, and trimetallic copper and silver complexes were synthesized with this ligand. The hybrid character of the ligand led to compounds with rich luminescence properties. These include coumarin-based blue fluorescence, observed as a sole emission in solution at room temperature, and green phosphorescence, which is efficient at low temperatures and dominates the spectra of the metal complexes. In the rigid environment of frozen solutions, the green phosphorescence shows an unusually long (for metal complexes) decay on the seconds timescale in high quantum yield. In addition, a red phosphorescence, which may be assigned to the triplet state localized in the phosphine-M 3 Cl 2 (M=Cu, Ag), is observed for the trinuclear complexes at low temperature. Neither the second-long phosphorescence nor the red emission is observed for the coumarin ligand, thus they must be a result of the coordination to coinage metal clusters. The excited states in these compounds were also investigated by femtosecond transient absorption spectroscopy and quantum chemical calculations.

The reactivity of the formazanate potassium salt [LtBuK(thf) (LtBu = PhNNC(4‐tBuPh)NNPh) with the group 14 chlorotetrylenes [{PhC(tBuN)2}ECl] (E = Si, Ge, Sn) was investigated. Three corresponding compounds with unique configurations were formed, demonstrating the diverse reactivity of the system. In addition to the anticipated salt metathesis reactions of the potassium salt with the chlorine function of tetrylenes, unexpected reduction/insertion steps into the N=N bond of the formazanate (Si, Ge) and subsequent C−H activation (Ge) were also observed. Furthermore, when the neutral formazan ligand [LtBuH] was exposed to silylenes [{PhC(tBuN)2}SiCl] and [LPhSiNMePy], substitution and addition reactions occurred. These discoveries significantly enrich the diversity of formazanate/formazan redox chemistry, opening up new avenues for exploration in this field.

The afterglow of coinage metal complexes synthesized by using novel coumarin‐functionalized aminodiphosphine ligands is depicted. A hybrid character of the ligand led to compounds with afterglow luminescence at low temperatures, which is clearly visible to the naked eye after the UV excitation is turned off. More information can be found in the Research Article by P. W. Roesky and co‐workers (DOI: 10.1002/chem.202300497). Artwork: Vanitha Reddy Naina and Lakshmi Prabha Edappilly.