Molten Salt-Assisted Synthesis of Titanium Nitride.

Titanium nitride is an exciting plasmonic material, with optical properties similar to gold. However, synthesizing TiN nanocrystals is highly challenging and typically requires solid-state reactions at very high temperatures (800-1000°C). Here, the synthesis of TiN nanocrystals is achieved at temperatures as low as 350°C, in just 1 h. The strategy comprises molten salt, Mg as reductant and Ca3N2 as nitride source. This brings TiN from the realm of solid-state chemistry into the field of solution-based synthesis in regular, borosilicate glassware.

The Chemistry of Cu3 N and Cu3 PdN Nanocrystals.

The precursor conversion chemistry and surface chemistry of Cu3 N and Cu3 PdN nanocrystals are unknown or contested. Here, we first obtain phase-pure, colloidally stable nanocubes. Second, we elucidate the pathway by which copper(II) nitrate and oleylamine form Cu3 N. We find that oleylamine is both a reductant and a nitrogen source. Oleylamine is oxidized by nitrate to a primary aldimine, which reacts further with excess oleylamine to a secondary aldimine, eliminating ammonia. Ammonia reacts with CuI to form Cu3 N. Third, we investigated the surface chemistry and find a mixed ligand shell of aliphatic amines and carboxylates (formed in situ). While the carboxylates appear tightly bound, the amines are easily desorbed from the surface. Finally, we show that doping with palladium decreases the band gap and the material becomes semi-metallic. These results bring insight into the chemistry of metal nitrides and might help the development of other metal nitride nanocrystals.

Precursor chemistry of metal nitride nanocrystals.

Metal nitride nanocrystals are a versatile class of nanomaterials. Depending on their chemical composition, the optical properties vary from those of traditional semiconductor nanocrystals (called quantum dots) to more metallic character (featuring a plasmon resonance). However, the synthesis of colloidal metal nitride nanocrystals is challenging since the underlying precursor chemistry is much less developed compared to the chemistry of metal, metal chalcogenide or metal phosphide nanocrystals. Here, we review chemical approaches that lead (or could lead) to the formation of colloidally stable metal nitride nanocrystals. By systematically comparing different synthetic approaches, we uncover trends and gain insight into the chemistry of these challenging materials. We also discuss and critically evaluate the plausibility of certain suggested mechanisms. This review is meant as a guide for the further development of colloidal nitride nanocrystals.

Resorcin[4]arene-based multidentate phosphate ligands with superior binding affinity for nanocrystal surfaces.

We designed and synthesized two resorcin[4]arene scaffolds with four phosphate binding groups. The ligands effectively bind in at least a tridentate fashion at low surface coverage. The superior binding affinity is demonstrated using solution NMR spectroscopy and exceeds that of single phosphonates.

Design and Synthesis of Luminescent Lanthanide-Based Bimodal Nanoprobes for Dual Magnetic Resonance (MR) and Optical Imaging.

Current biomedical imaging techniques are crucial for the diagnosis of various diseases. Each imaging technique uses specific probes that, although each one has its own merits, do not encompass all the functionalities required for comprehensive imaging (sensitivity, non-invasiveness, etc.). Bimodal imaging methods are therefore rapidly becoming an important topic in advanced healthcare. This bimodality can be achieved by successive image acquisitions involving different and independent probes, one for each mode, with the risk of artifacts. It can be also achieved simultaneously by using a single probe combining a complete set of physical and chemical characteristics, in order to record complementary views of the same biological object at the same time. In this scenario, and focusing on bimodal magnetic resonance imaging (MRI) and optical imaging (OI), probes can be engineered by the attachment, more or less covalently, of a contrast agent (CA) to an organic or inorganic dye, or by designing single objects containing both the optical emitter and MRI-active dipole. If in the first type of system, there is frequent concern that at some point the dye may dissociate from the magnetic dipole, it may not in the second type. This review aims to present a summary of current activity relating to this kind of dual probes, with a special emphasis on lanthanide-based luminescent nano-objects.

Lewis versus Brønsted Acid Activation of a Mn(IV) Catalyst for Alkene Oxidation.

Lewis acid (LA) activation by coordination to metal oxido species has emerged as a new strategy in catalytic oxidations. Despite the many reports of enhancement of performance in oxidation catalysis, direct evidence for LA-catalyst interactions under catalytically relevant conditions is lacking. Here, we show, using the oxidation of alkenes with H2O2 and the catalyst [Mn2(µ-O)3(tmtacn)2](PF6)2 (1), that Lewis acids commonly used to enhance catalytic activity, e.g., Sc(OTf)3, in fact undergo hydrolysis with adventitious water to release a strong Brønsted acid. The formation of Brønsted acids in situ is demonstrated using a combination of resonance Raman, UV/vis absorption spectroscopy, cyclic voltammetry, isotope labeling, and DFT calculations. The involvement of Brønsted acids in LA enhanced systems shown here holds implications for the conclusions reached in regard to the relevance of direct LA-metal oxido interactions under catalytic conditions.