This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo‐copper precursor, mesitylcopper(I) [CuMes]z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2O or Cu2S nanoparticles. Use of sub‐stoichiometric quantities of protonated ligand (pro‐ligand; 0.1–0.2 equivalents vs. [CuMes]z) allows saturation of surface coordination sites but avoids excess pro‐ligand contaminating the nanoparticle solutions. The pro‐ligands are nonanoic acid (HO2CR1), 2‐[2‐(2‐methoxyethoxy)ethoxy]acetic acid (HO2CR2) or di(thio)nonanoic acid, (HS2CR1), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2O is preferentially coordinated by carboxylate ligands and Cu2S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well‐defined nanoparticles and the need for appropriate ligand selection.

Intercalation of organic anions into 2D materials can enable exfoliation, improve dispersion stability, increase surface area, and provide useful functional groups. In layered metal hydroxides, intercalation of bulk structures is commonly achieved by cumbersome and typically incomplete anion exchange reactions. In contrast, here, a series of carboxylate-intercalated layered zinc hydroxides (LZH-R) are synthesized directly, at room temperature, by reacting an organozinc reagent with a precise sub-stoichiometric quantity of the desired carboxylic acid and water. A range of carboxylic acids are used to make new LZH-R materials which are crystalline, soluble, and functionalized, as established by X-ray diffraction, spectroscopic, and microscopy techniques. When R is an alkyl ether carboxylate, this direct synthesis method results in the spontaneous exfoliation of the LZH-R into monolayer nanosheets with high yields (70-80%) and high solubilities in alcohols and water of up to 180 mg mL −1 . By altering the carboxylate ligand, functional groups suitable for post-synthetic modification or for detection by fluorescence are also introduced. These examples demonstrate a versatile synthetic route for functional exfoliated nanosheets.

In article number 2102631, Milo S. P. Shaffer, Charlotte K. Williams, and co‐workers present a direct and versatile organometallic route to carboxylate‐intercalated layered zinc hydroxide (LZH) 2D nanosheets. The functional LZHs show excellent solubility in polar solvents, including water with solubilities of up to 140 mg mL−1 and monolayer exfoliation yields of 70–80%. This method contrasts with more conventional top‐down routes to layered metal hydroxides and offers unique insight into the mechanisms of seeding, growth, and exfoliation of 2D materials.