Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity

Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO.     

Transition‐Metal‐Catalyzed Oxidation of Metallic Sn in NiO/SnO2 Nanocomposite

It is well accepted that metallic tin as a discharge (reduction) product of SnO_x cannot be electrochemically oxidized below 3.00 V versus Li⁺/Li⁰ due to the high stability of Li₂O, though a similar oxidation can usually occur for a transition metal formed from the corresponding oxide. In this work, nanosized Ni₂SnO₄ and NiO/SnO₂ nanocomposite were synthesized by coprecipitation reactions and subsequent heat treatment. Owing to the catalytic effect of nanosized metallic nickel, metallic tin can be electrochemically oxidized to SnO₂ below 3.00 V. As a result, the reversible lithium‐storage capacities of the nanocomposite reach 970 mAh g^?1 or above, much higher than the theoretical capacity (ca. 750 mAh g^?1) of SnO₂, NiO, or their composites. These findings extend the well‐known electrochemical conversion reaction to non‐transition‐metal compounds and may have important applications, for example, in constructing high‐capacity electrode materials and efficient catalysts.     

Synthesis and Characterization of Ag8(Ge1−x,Snx)(S6−y,Sey) Colloidal Nanocrystals

A facile colloidal approach to synthesize Ag₈(Ge_1?x,Sn_x)(S_6?y,Se_y) nanocrystals (NCs) in a highly controlled way across the entire compositional ranges (0≤x≤1, 0≤y≤6) has been developed. The NCs exhibit a uniform size distribution, highly crystalline structure, over 1 g scalable synthesis, and tunable band gaps in the range of 0.88–1.45 eV by varying their chemical compositions. The Ag₈GeS₆ NCs with a band gap of approximately 1.45 eV were employed as a model light harvester to assess their applicability in solar cells by a full solution‐processing device, yielding an efficiency of 0.28 % under AM1.5 illumination, demonstrating their application potential in solar energy utilization.     

Chemical and Toxicological Investigations of a Previously Unknown Poisonous European Mushroom Tricholoma terreum

The established tradition of consuming and marketing wild mushrooms has focused attention on mycotoxicity, which has become a global issue. In the present study, we describe the toxins found in a previously unknown poisonous European mushroom Tricholoma terreum. Fifteen new triterpenoids terreolides A–F ( 1 – 6 ) and saponaceolides H–P ( 8 – 16 ) were isolated from the fruiting bodies of the toxic mushroom T. terreum. Terreolides A–C ( 1 – 3 ) possessed a unique 5/6/7 trioxaspiroketal system, whereas terreolides D–F ( 4 – 6 ) possessed an unprecedented carbon skeleton. Two abundant compounds in the mushroom, saponaceolide B ( 7 ) and saponaceolide M ( 13 ), displayed acute toxicity, with LD₅₀ values of 88.3 and 63.7 mg kg^?1 when administered orally in mice. Both compounds were found to increase serum creatine kinase levels in mice, indicating that T. terreum may be the cause of mushroom poisoning ultimately leading to rhabdomyolysis.     

Experimental and Computational Studies of a Multi‐Electron Donor–Acceptor Ligand Containing the Thiazolo[5,4‐d]thiazole Core and its Incorporation into a Metal–Organic Framework

A ligand containing the thiazolo[5,4‐d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N′‐(thiazolo[5,4‐d]thiazole‐2,5‐diylbis(4,1‐phenylene))bis(N‐(pyridine‐4‐yl)pyridin‐4‐amine ( 1 ), was designed as a donor–acceptor system for incorporation into electronically active metal–organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis‐near‐infrared spectroelectrochemistry (UV/Vis‐NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge‐transfer interactions between the terminal triarylamine moieties upon oxidation, whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi‐electron donor–acceptor ligand into a new two‐dimensional MOF, [Zn(NO₃)₂( 1 )] ( 2 ), resulted in an inhibition of the oxidation processes, but retention of the reduction capability of 1 . Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation.     

Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation

The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O^?.) is an important species in C?H activation. The mechanistic details of C?H activation by O^?. radicals can be well understood by studying the reactions between O^?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc₂O₃)_NO^? (N=1–18) clusters was observed. The reactivity of (Sc₂O₃)_NO^? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc₈O₁₃^?) and 12 (Sc₂₄O₃₇^?). Larger (Sc₂O₃)_NO^? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc₂O₃)_NO^? (N=1–5) clusters, which were found to contain the O^?. radicals as the active sites. The local charge environment around the O^?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O^?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation.     

A New Class of Tunable Dendritic Diphosphine Ligands: Synthesis and Applications in the Ru‐Catalyzed Asymmetric Hydrogenation of Functionalized Ketones

A series of tunable G₀–G₃ dendritic 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) ligands was prepared by attaching polyaryl ether dendrons onto the four phenyl rings on the P atoms. Their ruthenium complexes were employed in the asymmetric hydrogenation of β‐ketoesters, α‐ketoesters, and α‐ketoamides to reveal the effects of dendron size on the catalytic properties. The second‐ and third‐generation catalysts exhibited excellent enantioselectivities, which are remarkably higher than those obtained from the small molecular catalysts and the first‐generation catalyst. Molecular modeling indicates that the incorporation of bulky dendritic wedges can influence the steric environments around the metal center. In addition, the ruthenium catalyst bearing a second‐generation dendritic ligand could be recycled and reused seven times without any obvious decrease in enantioselectivity.     

Metal‐Free Oxidative Radical Addition of Carbonyl Compounds to α,α‐Diaryl Allylic Alcohols: Synthesis of Highly Functionalized Ketones

A metal‐free direct alkylation of simple carbonyl compounds (ketones, esters, and amides) with α,α‐diaryl allylic alcohols is described. The protocol provides facile access to highly functionalized dicarbonyl ketones by a radical addition/1,2‐aryl migration cascade. The regioselectivity of the reaction was precisely controlled by the nature of the carbonyl compound.     

Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide

A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO₂ under very mild conditions (1 atm CO₂, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high M_n value of 28 600 and a relatively narrow polydispersity (M_w/M_n ratio) of 1.43 were also achieved.     

Interfacial Chiral Selection by Bulk Species

A chiral selection process in a self‐assembled soft monolayer of an achiral amphiphile as a consequence of its interaction with chiral species dissolved in the aqueous subphase, is reported. The extent of the chiral selection is statistically measured in terms of the enantiomorphic excess of self‐assembled submillimeter domains endowed with well‐defined orientational chirality that is unambiguously resolved using optical microscopy. Our results show that the emergence of chirality is mediated by electrostatic interactions and significantly enhanced by hydrophobic effects. This chiral chemical effect can be suppressed and even reversed by opposing a macroscopic physical influence, such as vortical stirring. This result gives evidence for the crucial role of hydrodynamic effects in supramolecular aggregation.