Electrochemical and Scalable Dehydrogenative C(sp3)−H Amination via Remote Hydrogen Atom Transfer in Batch and Continuous Flow

A hydrogen atom transfer-directed electrochemical intramolecular C−H amination has been developed in which the N-radical species are generated at the anode, and the base required for the reaction is generated at the cathode. A broad range of valuable pyrrolidines were prepared in good yields and with high chemoselectivity. The reaction was easily scaled up in both batch and continuous flow systems.     

Optoelectronic,Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λ_max=427–464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended π-conjugated groups cause a redshift, whereas electron-withdrawing groups result in a blueshift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λ_PL=525–578 nm) with quantum yields of up to 18 % and lifetimes of 1.1–1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (E_ox1=0.62–1.02 V vs. Fc/Fc⁺) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state.     

Chemical and Electrochemical Lithiation of van der Waals Tetrel-Arsenides

Lithiation of van der Waals tetrel-arsenides, GeAs and SiAs, has been investigated. Electrochemical lithiation demonstrated large initial capacities of over 950 mAh g⁻¹ accompanied by rapid fading over successive cycling in the voltage range 0.01–2 V. Limiting the voltage range to 0.5–2 V achieved more stable cycling, which was attributed to the intercalation process with lower capacities. Ex situ powder X-ray diffraction confirmed complete amorphization of the samples after lithiation, as well as recrystallization of the binary tetrel-arsenide phases after full delithiation in the voltage range 0.5–2 V. Solid-state synthetic methods produce layered phases, in which Si-As or Ge-As layers are separated by Li cations. The first layered compounds in the corresponding ternary systems were discovered, Li_0.9Ge_2.9As_3.1 and Li₃Si₇As₈, which crystallize in the Pbam (No. 55) and P2/m (No. 10) space groups, respectively. Semiconducting layered GeAs and SiAs accommodate the extra charge from Li cations through structural rearrangement in the Si-As or Ge-As layers and eventually by replacement of the tetrel dumbbells with sets of Li atoms. Ge and Si monoarsenides demonstrated high structural flexibility and a mild ability for reversible lithiation.     

The Hydrogen Bond and Beyond: Perspectives for Rotational Investigations of Non-Covalent Interactions

In the last decade, experiment and theory have expanded our vision of non-covalent interactions (NCIs), shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. Whereas most experimental data originate from condensed phases, the introduction of broadband (chirped-pulse) microwave fast-passage techniques has revolutionized the field of rotational spectroscopy, offering unexplored avenues for high-resolution studies in the gas phase. We present an outlook of hot topics for rotational investigations on isolated intermolecular clusters generated in supersonic jet expansions. Rotational spectra offer very detailed structural data, easily discriminating the isomeric or isotopic composition and effectively cancelling any solvent, crystal, or matrix bias. The direct comparison with quantum mechanical predictions provides insight into the origin of the inter- and intramolecular interactions with much greater precision than any other spectroscopic technique, simultaneously serving as test-bed for fine-tuning of theoretical methods. We present recent examples of rotational investigations around three topics: oligomer formation, chiral recognition, and identification of halogen, chalcogen, pnicogen, or tetrel bonds. The selected examples illustrate the benefits of rotational spectroscopy for the structural and energetic assessment of inter-/intramolecular interactions, which may help to move from fundamental research to applications in supramolecular chemistry and crystal engineering.     

Asymmetric Reactions involving Lewis Base Catalyst Tethered Dearomatized Intermediates

Numerous protocols have been developed for the functionalization of aromatic substances. Among them, the strategy by which aromatic substrates are activated in situ to generate dearomatized intermediates is highly efficient but challenging, especially in the field of asymmetric catalysis. In this Concept article, the application of some well-established chiral Lewis base catalysis, including primary/secondary amines and N-heterocyclic carbenes, that can covalently form catalyst-tethered dearomatized ortho/para-quinodimethane species with diverse heteroaryl and aryl carbonyl substrates is summarized in a number of asymmetric cycloaddition and addition reactions with diverse reagents generally having electrophilic properties. As a result, a variety of enantioenriched aromatic products with higher molecular complexity are constructed effectively through a rearomatization process.     

Beyond Biological Chelation: Coordination of f-Block Elements by Polyhydroxamate Ligands

The promise of polyhydroxamic acid ligands for the selective chelation of the f-block elements is becoming increasingly more apparent. The initial studies of polyhydroxamic acid siderophores showed the formation of highly stable complexes with Pu^IV, but a higher preference for Fe^III hindered effective applications. The development of synthetic routes toward highly pure and customizable ligands containing multiple hydroxamic acids allowed for the growth of new classes of compounds. Although the first round of these ligands focused on the incorporation of siderophore-like frameworks, the new synthetic strategies led to small molecules of various frameworks and even resins for applications in the field of f-block element separations and biological desorption. Unfortunately, a lack of consistent stability-constant data makes direct comparisons across this body of work difficult. More studies into the stability constants and separations of the f-block elements in a variety of pH ranges is necessary to truly realize the potential for polyhydroxamic acid ligands.     

Actinide Organometallic Complexes with π-Ligands

Recent developments and results from the organometallic chemistry of the actinides are reviewed. In the last one and a half years the structural data of about 15 organometallic complexes of transuranium actinides (Np or Pu) have been published, all involving π-ligands in the coordination sphere of the metal ion. On the basis of these data, a comparison of these molecules is presented. Depending on the steric demands of the ligands, effects like the actinide contraction seem to be stronger or weaker in the structural features. This indicates that the interplay between the actinide ion and the π-ligand is rather flexible, enabling the formation of stable bonds over a broad range of actinide ion oxidation states.     

Protein–Metal-Ion Networks: A Unique Approach toward Metal Sulfide Nanoparticles Embedded In Situ in Nanocomposites

Nanoscale metal sulfides are of tremendous potential in biomedicine. Generally, the properties and performances of metal sulfide nanoparticles (NPs) are highly related to their structures, sizes and morphologies. Recently, a strategy of using sulfur-containing protein–metal-ion networks for preparing metal sulfide embedded nanocomposites was proposed. Within the networks, proteins can play multiple roles to drive the transformation of these networks into protein-encapsulated metal sulfide NPs with ultrasmall size and defined structure (as both a template and a sulfur provider) or metal sulfide NP–protein hydrogels with injecting and self-healing properties (as a template, a sulfur provider, and a gelator) in a controlled manner. In this Concept, the synthesis strategy, the formation mechanism, and the biomedical applications of the gained nanocomposites are presented. Moreover, the challenges and opportunities of using protein–metal ion networks to construct functional materials for biomedical applications are analyzed.     

Beyond Common Metal–Metal Bonds, κ3-Bis(donor)ferrocenyl→Transition-Metal Interactions

Ligands with 1,1′-bis(donor)ferrocene motif are capable of a wide range of binding modes, including the trans chelation mode in which there is a Fe−M interaction (κ³-D,Fe,D), in the form of a dative Fe→TM bond (TM=transition metal). This Minireview will explore the nature of this Fe–TM interaction thorough select examples as well as how to characterize a Fe→TM dative bond using physical, computational, and spectroscopic techniques.