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Polymer electrolytes play a crucial role in advancing rechargeable magnesium batteries (RMBs) owing to their exceptional characteristics, including high flexibility, superior interface compatibility, broad electrochemical stability window, and enhanced safety features. Despite these advantages, research in this domain remains nascent, plagued by single preparation approaches and challenges associated with the compatibility between polymer electrolytes and Mg metal anode. In this study, we present a novel synthesis strategy to fabricate a glycerol α,α′‐diallyl ether‐3,6‐dioxa‐1,8‐octanedithiol‐based composite gel polymer electrolyte supported by glass fiber substrate (GDT@GF CGPE) through anion modification and thiol‐ene click chemistry polymerization. The developed route exhibits novelty and high efficiency, leading to the production of GDT@GF CGPEs featuring exceptional mechanical properties, heightened ionic conductivity, elevated Mg2+ transference number, and commendable compatibility with Mg anode. The assembled modified Mo6S8||GDT@GF||Mg cells exhibit outstanding performance across a wide temperature range and address critical safety concerns, showcasing the potential for applications under extreme conditions. Our innovative preparation strategy offers a promising avenue for the advancement of polymer electrolytes in high‐performance rechargeable magnesium batteries, while also opens up possibilities for future large‐scale applications and the development of flexible electronic devices. [ABSTRACT FROM AUTHOR]

Integrating controllable spin states into single‐molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d–4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4) ⋅ 4H2O (H2quinha=quinaldichydroxamic acid, HClsal=5‐chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post‐synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4) ⋅ 3H2O (HClsaldt=4‐chloro‐2‐(1,3‐dithiolan‐2‐yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination‐induced spin state switching (CISSS) took place with spin state altering from low‐spin S=0 to high‐spin S=1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm−1 to 423 cm−1, along with hysteresis opening and an over 200‐fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire‐new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach. [ABSTRACT FROM AUTHOR]

We report the synthesis of a longitudinally helical molecular nanocarbon, hexabenzoheptacene (HBH), along with its dimethylated derivative (HBH‐Me), which are composed of six benzene rings periodically benzannulated to both zigzag edges of a heptacene core. This benzannulation pattern endows the resulting nanocarbons with a helical heptacene core and local aromaticity, imparting enhanced solubility and stability to the system. The chiral HBH‐Me adopts a more highly twisted conformation with an end‐to‐end twist angle of 95°, enabling the separation of the enantiomers. Both HBH and HBH‐Me can be facilely oxidized into their corresponding dications, which exhibit enhanced planarity and aromaticity upon loss of electrons. Notably, both longitudinally helical nanocarbons readily promote solid state packing into two‐dimensional (2D) arrangement. Single‐crystal microbelts of HBH‐Me show hole mobility up to 0.62 cm2 V−1 s−1, illustrating the promising potential of these longitudinally helical molecules for organic electronic devices. [ABSTRACT FROM AUTHOR]

The large size of K‐ion makes the pursuit of stable high‐capacity anodes for K‐ion batteries (KIBs) a formidable challenge, particularly for high temperature KIBs as the electrode instability becomes more aggravated with temperature climbing. Herein, we demonstrate that a hollow ZnS@C nanocomposite (h‐ZnS@C) with a precise shell modulation can resist electrode disintegration to enable stable high‐capacity potassium storage at room and high temperature. Based on a model electrode, we identify an interesting structure‐function correlation of the h‐ZnS@C: with an increase in the shell thickness, the cyclability increases while the rate and capacity decrease, shedding light on the design of high‐performance h‐ZnS@C anodes via engineering the shell thickness. Typically, the h‐ZnS@C anode with a shell thickness of 60 nm can deliver an impressive comprehensive performance at room temperature; the h‐ZnS@C with shell thickness increasing to 75 nm can achieve an extraordinary stability (88.6 % capacity retention over 450 cycles) with a high capacity (450 mAh g−1) and a superb rate even at an extreme temperature of 60 °C, which is much superior than those reported anodes. This contribution envisions new perspectives on rational design of functional metal sulfides composite toward high‐performance KIBs with insights into the significant structure‐function correlation. [ABSTRACT FROM AUTHOR]

Rigid three‐dimensional (3D) polycyclic propellanes have garnered interest due to their unique conformational spaces, which display great potential use in selectivity, separation and as models to study through‐space electronic interactions. Herein we report the synthesis of a novel rigid propellane, trinaphtho[3.3.3]propellane triimide, which comprises three imide groups embedded on a trinaphtho[3.3.3]propellane. This propellane triimide exhibits large bathochromic shift, amplified molar absorptivity, enhanced fluorescence, and lower reduction potential when compared to the subunits. Computational and experimental studies reveal that the effective through‐space π‐orbitals interacting (homoconjugation) occurs between the subunits. Single‐crystal XRD analysis reveals that the propellane triimide has a highly quasi‐D3h symmetric skeleton and readily crystallizes into different superstructures by changing alkyl chains at the imide positions. In particular, the porous 3D superstructure with S‐shaped channels is promising for taking up ethane (C2H6) with very good selectivity over ethylene (C2H4), which can purify C2H4 from C2H6/C2H4 in a single separation step. This work showcases a new class of rare 3D polycyclic propellane with intriguing electronic and supramolecular properties. [ABSTRACT FROM AUTHOR]

Hollow nanoporous carbon architectures (HNCs) present significant utilitarian value for a wide variety of applications. Facile and efficient preparation of HNCs has long been pursued but still remains challenging. Herein, we for the first time demonstrate that single‐component metal–organic frameworks (MOFs) crystals, rather than the widely reported hybrid ones which necessitate tedious operations for preparation, could enable the facile and versatile syntheses of functional HNCs. By controlling the growth kinetics, the MOFs crystals (STU‐1) are readily engineered into different shapes with designated styles of crystalline inhomogeneity. A subsequent one‐step pyrolysis of these MOFs with intraparticle difference can induce a simultaneous self‐hollowing and carbonization process, thereby producing various functional HNCs including yolk‐shell polyhedrons, hollow microspheres, mesoporous architectures, and superstructures. Superior to the existing methods, this synthetic strategy relies only on the complex nature of single‐component MOFs crystals without involving tedious operations like coating, etching, or ligand exchange, making it convenient, efficient, and easy to scale up. An ultra‐stable Na‐ion battery anode is demonstrated by the HNCs with extraordinary cyclability (93 % capacity retention over 8000 cycles), highlighting a high level of functionality of the HNCs. [ABSTRACT FROM AUTHOR]

Multicomponent supramolecular block copolymers (BCPs) have attracted much attention due to their potential functionalities, but examples of three‐component supramolecular BCPs are rare. Herein, we report the synthesis of three‐component multiblock 1D supramolecular copolymers of Ir(III) complexes 1–3 by a sequential seeded supramolecular polymerization approach. Precise control over the kinetically trapped species via the pathway complexity of the monomers is the key to the successful synthesis of BCPs with up to 9 blocks. Furthermore, 5‐block BCPs with different sequences could be synthesized by changing the addition order of the kinetic species during a sequentially seeded process. The corresponding heterogeneous nucleation‐elongation process has been confirmed by the UV/Vis absorption spectra, and each segment of the multiblock copolymers could be characterized by both TEM and SEM. Interestingly, the energy transfer leads to weakened emission of 1‐terminated and enhanced emission of 3‐terminated BCPs. This study will be an important step in advancing the synthesis and properties of three‐component BCPs. [ABSTRACT FROM AUTHOR]

Spin crossover (SCO) materials with new architectures will expand and enrich the research in the SCO field. Here, we report two metal–organic frameworks (MOFs) containing tetradentate organic ligands and hexatopic linkers [Ag8X8(CN)6]6− (X=Br and I), which represents the first SCO MOF with clusters as building blocks. The silver halide cluster can be further removed after reacting with lithium tetracyanoquinodimethan (LiTCNQ). Such post‐synthetic modification (PSM) is realized via single‐crystal to single‐crystal (SCSC) transformation from urk to nbo topology. Accordingly, the spin state and fluorescence properties are greatly modified by cluster deconstruction. Therefore, these achievements will provide new ideas for the design of new SCO systems and the development of PSM methods. [ABSTRACT FROM AUTHOR]

The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal‐nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that the metal‐nitrogen coupling in anti‐perovskite Co4N can be effective modulated by Cu doping to form Co3CuN, leading to strongly promoted hydrogenation process during electrochemical reduction of nitrate (NO3−RR) to ammonia. The combination of advanced spectroscopic techniques and density functional theory calculations reveal that Cu dopants strengthen the Co−N bond and upshifted the metal d‐band towards the Fermi level, promoting the adsorption of NO3− and *H and facilitating the transition from *NO2/*NO to *NO2H/*NOH. Consequently, the Co3CuN delivers noticeably better NO3−RR activity than the pristine Co4N, with optimal Faradaic efficiency of 97 % and ammonia yield of 455.3 mmol h−1 cm−2 at −0.3 V vs. RHE. This work provides an effective strategy for developing high‐performance heterogeneous catalyst for electrochemical synthesis. [ABSTRACT FROM AUTHOR]

Supramolecular copolymers have attracted much attention due to their potential functionalities. However, the co‐assembly strategies to construct co‐assemblies of small molecules with well‐defined sequence structures are still limited, especially for more complex crystalline block co‐assemblies. Herein, we target this challenge by designing IrIII complexes 1 and 2, which possess unique self‐assembly pathways and are capable of forming crystalline assemblies in aqueous systems. Specifically, block and random co‐assemblies of 1 and 2 can be synthesized by kinetic and thermodynamic control, respectively. Meanwhile, by adjusting the water content to orthogonalize the on‐pathway and the off‐pathway, an unprecedented pathway‐switching approach is realized to synthesize block and random co‐assemblies. By coupling the kinetic pathways, the present co‐assembly strategies are expected to pave the way for the synthesis of crystalline co‐assemblies of small molecules and the construction of organic heterostructures. [ABSTRACT FROM AUTHOR]

Post‐polymerization modification (PPM) offers a versatile approach for engineering multifunctional polymers, but this advantage has not been fully exploited to fabricate multifunctional liquid crystal polymers (LCPs). Here, we design a facile synthetic approach towards multifunctional LCP by combining the ring‐opening metathesis polymerization (ROMP) with PPM, in which ROMP helps to prepare a reactive LCP precursor with high molecular weight, and PPM provides a facilitation to introduce functional groups into the precursor. Consequently, a photo‐ and humidity‐responsive linear LCP (LLCP) is demonstrated to show the potential of this synthetic strategy to diversify functions of the LCPs. Under light irradiation and humidity changes, the deformation modes of the LLCP films are converted to complex shapes (bending, twisting, and curling). The obtained dual‐responsive LLCP with high molecular weight possesses excellent processability and recyclability, making it possible to construct 3D shape actuators with programmable deformation behaviors under light/humidity. [ABSTRACT FROM AUTHOR]

Mimicking natural nitrogenase to create highly efficient single‐atom catalysts (SACs) for ambient N2 fixation is highly desired, but still challenging. Herein, S‐coordinated Fe SACs on mesoporous TiO2 have been constructed by a lattice‐confined strategy. The extended X‐ray absorption fine structure and X‐ray photoelectron spectroscopy spectra demonstrate that Fe atoms are anchored in TiO2 lattice via the FeS2O2 coordination configuration. Theoretical calculations reveal that FeS2O2 sites are the active centers for electrocatalytic nitrogen reduction reaction (NRR). Moreover, the finite element analysis shows that confinement of opened and ordered mesopores can facilitate the mass transport and offer an enlarged active surface area for NRR. As a result, this catalyst delivers a favorable NH3 yield rate of 18.3 μg h−1 mgcat.−1 with a high Faradaic efficiency of 17.3 % at −0.20 V versus a reversible hydrogen electrode. Most importantly, this lattice‐confined strategy is universal and can also be applied to Ni1Sx@TiO2, Co1Sx@TiO2, Mo1Sx@TiO2, and Cu1Sx@TiO2 SACs. Our study provides new hints for the design and biomimetic synthesis of highly efficient NRR electrocatalysts. [ABSTRACT FROM AUTHOR]

Lei Zhang and his team have successfully synthesized a unique molecular carbon compound with a helical heptacene core and six benzene rings. This compound exhibits enhanced solubility and stability due to its local aromaticity, which is a result of the steric congestion caused by the benzannulation pattern. Additionally, the compound demonstrates excellent charge transport properties and forms a two-dimensional crystal structure. [Extracted from the article]

Stimuli‐responsive materials that can be reversibly switched by light are of immense interest. Among them, photo‐responsive spin crossover (SCO) complexes have great promises to combine the photoactive inputs with multifaceted outputs into switchable materials and devices. However, the reversible control the spin‐state change by photochromic guests is still challenging. Herein, we report an unprecedented guest‐driven light‐induced spin change (GD‐LISC) in a Hofmann‐type metal–organic framework (MOF), [Fe(bpn){Ag(CN)2}2]⋅azobenzene. (1, bpn=1,4‐bis(4‐pyridyl)naphthalene). The reversible trans–cis photoisomerization of azobenzene guest upon UV/Vis irradiation in the solid‐state results in the remarkable magnetic changes in a wide temperature range of 10–180 K. This finding not only establishes a new switching mechanism for SCO complexes, but also paves the way toward the development of new generation of photo‐responsive magnetic materials. [ABSTRACT FROM AUTHOR]

Here we reported the deuteration of the metal‐binding equatorial water molecules in a reported HoIII single‐molecule magnet (SMM) with pentagonal‐bipyramidal geometry, from [Ho(CyPh2PO)2(H2O)5]3+ to [Ho(CyPh2PO)2(D2O)5]3+. The hyperfine structures originating from the nuclear spin of 165HoIII can be clearly observed. Moreover, the resulting magnetization dynamics revealed the switch of the relative relaxation rates for the two isotope‐isomorphic complexes—respectively faster/slower at low/high temperature. The noticeable isotope effect arises from not only the paramagnetic metal center but also the diamagnetic ligands, which can be explained by the ab initio calculated tunnel splitting and the involvement of the super‐hyperfine interaction related to the difference in the nuclear spin number of protium (1H, I=1/2) and deuterium (2H, I=1). [ABSTRACT FROM AUTHOR]

Combining Ising‐type magnetic anisotropy with collinear magnetic interactions in single‐molecule magnets (SMMs) is a significant synthetic challenge. Herein we report a Dy[15‐MCCu‐5] (1‐Dy) SMM, where a DyIII ion is held in a central pseudo‐D5h pocket of a rigid and planar Cu5 metallacrown (MC). Linking two Dy[15‐MCCu‐5] units with a single hydroxide bridge yields the double‐decker {Dy[15‐MCCu‐5]}2 (2‐Dy) SMM where the anisotropy axes of the two DyIII ions are nearly collinear, resulting in magnetic relaxation times for 2‐Dy that are approximately 200 000 times slower at 2 K than for 1‐Dy in zero external field. Whereas 1‐Dy and the YIII‐diluted Dy@2‐Y analogue do not show remanence in magnetic hysteresis experiments, the hysteresis data for 2‐Dy remain open up to 6 K without a sudden drop at zero field. In conjunction with theoretical calculations, these results demonstrate that the axial ferromagnetic Dy–Dy coupling suppresses fast quantum tunneling of magnetization (QTM). The relaxation profiles of both complexes curiously exhibit three distinct exponential regimes, and hold the largest effective energy barriers for any reported d–f SMMs up to 625 cm−1. [ABSTRACT FROM AUTHOR]

Aqueous organic redox flow batteries (AORFBs) have received considerable attention for large‐scale energy storage. Quinone derivatives, such as 9,10‐anthraquinone‐2,7‐disulphonic acid (2,7‐AQDS), have been explored intensively owing to potentially low cost and swift reaction kinetics. However, the low solubility in pH‐neutral electrolytes restricts their application to corrosive acidic or caustic systems. Herein, the single molecule redox‐targeting reactions of 2,7‐AQDS anolyte are presented to circumvent its solubility limit in pH‐neutral electrolytes. Polyimide was employed as a low‐cost high‐capacity solid material to boost the capacity of 2,7‐AQDS electrolyte to 97 Ah L−1. Through in situ FTIR spectroscopy, a hydrogen‐bonding mediated reaction mechanism was disclosed. In conjunction with NaI as catholyte and nickel hexacyanoferrate as the catholyte capacity booster, a single‐molecule redox‐targeting reaction‐based full cell with energy density up to 39 Wh L−1 was demonstrated. [ABSTRACT FROM AUTHOR]

CO adlayers on Pt(111) electrode surfaces are an important electrochemical system and of great relevance to electrocatalysis. The potential‐dependent structure and dynamics of these adlayers are complex and still controversial, especially in the CO pre‐oxidation regime. We here employ in situ high‐speed scanning tunneling microscopy for studying the surface phase behavior in CO‐saturated 0.1 m H2SO4 on the millisecond time scale. At potentials near the onset of CO pre‐oxidation local fluctuations in the (2×2)‐CO adlayer are observed, which increase towards more positive potentials. Above 0.20 V (vs. Ag/AgCl), this leads to an adlayer where COad apparently reside on every top site, but still exhibit a (2×2) superstructure modulation. We interpret this observation as a dynamic effect, caused by a small number of highly mobile point defects in the (2×2)‐CO adlayer. As shown by density functional theory calculations, the CO lattice near such defects relaxes into a local (1×1) arrangement, which can rapidly propagate across the surface. This scenario, where a static (2×2) COad sublattice coexists with a highly dynamic sublattice of partially occupied top sites, explains the pronounced COad surface mobility during electrooxidation. [ABSTRACT FROM AUTHOR]

The role of endogenous serotonin (5‐HT) in gastrointestinal motility is still highly controversial. Although electrochemical techniques allow for direct and real‐time recording of biomolecules, the dynamic monitoring of 5‐HT release from elastic and tubular intestine during motor reflexes remains a great challenge because of the specific peristalsis patterns and inevitable passivation of the sensing interface. A stretchable sensor with antifouling and decontamination properties was assembled from gold nanotubes, titanium dioxide nanoparticles, and carbon nanotubes. The sandwich‐like structure endowed the sensor with satisfying mechanical stability and electrochemical performance, high resistance against physical adsorption, and superior efficiency in the photodegradation of biofouling molecules. Insertion of the sensor into the lumen of rat ileum (the last section of the small intestine) successfully mimics intestinal peristalsis, and simultaneous real‐time monitoring of distension‐evoked 5‐HT release was possible for the first time. Our results unambiguously reveal that mechanical distension of the intestine induces endogenous 5‐HT overflow, and 5‐HT level is closely associated with the physiological or pathological states of the intestine. [ABSTRACT FROM AUTHOR]

A cesium bismuth germanate, Cs2Bi2O(Ge2O7) (CBGO), was synthesized by a traditional high‐temperature solid‐state reaction. Its structure features a 3D network composed of a 1D chains composed of Bi2O8 dimers that are further bridged by Ge2O7 dimers, forming tunnels of seven member rings (MRs) that are filled by the Cs+ cations. CBGO exhibits extraordinary larger second harmonic generation (SHG) response of about 13.7 times that of KDP (KH2PO4) under 1064 nm laser radiation and 1.1 times that of KTP (KTiOPO4) under 2.05 μm laser radiation, which is the highest among all of the metal germanates reported so far. CBGO possesses a moderate birefringence (0.073 at 1064 nm) and is phase matchable. Furthermore, CBGO melts congruently and exhibits high thermal stability. [ABSTRACT FROM AUTHOR]

Abstraction of iodide from [(η5‐C5iPr5)2UI] (1) produced the cationic uranium(III) metallocene [(η5‐C5iPr5)2U]+ (2) as a salt of [B(C6F5)4]−. The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non‐negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to dominant relaxation by a Raman process. [ABSTRACT FROM AUTHOR]

An intriguing reversible band gap narrowing behavior of the lead‐free hybrid perovskite single crystal DMASnI3 (DMA=CH3NH2CH3+) from yellow to black is observed without phase transformation. We discuss the transformation mechanism in detail. More interestingly, the transformed samples in black can rapidly self‐heal into yellow ones when exposed to deionized water (DI water). Contrary to other hybrid perovskites, DMASnI3 crystals exhibit excellent water phase stability. For example, DMASnI3 was immersed in DI water for 16 h and no decomposition was observed. Inspired by its excellent water phase stability, we demonstrate a potential eco‐friendly application of DMASnI3 in photo‐catalysis for H2 evolution in DI water. We present the first H2 evolution rate of 0.64 μmol h−1 with good recycling properties for pure DMASnI3 crystals. After the narrowing process, the optical band gap of DMASnI3 can be lowered from 2.48 eV to 1.32 eV. Systematical characterizations are applied to investigate their structures and optoelectronic properties. The reversible band gap narrowing behavior and outstanding electrical properties, such as higher carrier mobility and long carrier lifetime show that DMASnI3 has a great potential for optoelectronic applications. Reversible band gap narrowing behavior of Sn‐based hybrid perovskite single crystal was first revealed with excellent phase stability, narrow band gap, higher carrier mobility and longer carrier lifetime. This is encouraging for the optoelectronic application. [ABSTRACT FROM AUTHOR]

Abstract: Like many branches of science, not to mention culture in general, electrochemistry has a number of recurring topics: Areas of research that are popular for a certain time, then fade away as their possibilities seem to have been exhausted, only to return decades later as progress in experimental or theoretical techniques offer new possibilities for their investigation. A prime example are fuel cells, which have undergone five such cycles, but here we discuss a general concept of kinetics—the pre‐exponential factor of a rate constant—which has undergone two such cycles. The first cycle was in the 1950–1980s, when the methods of electrochemical kinetics were developed, and the interpretation was based on transition‐state theory. The second was triggered by the re‐discovery of Kramers theory for reactions in condensed phases. This Minireview will show that the time has come for a third cycle based on recent progress in electrocatalysis. [ABSTRACT FROM AUTHOR]

Materials with hysteretic multi-step spin-crossover (SCO) have potential application in high-order data storage. Here, an unprecedented hysteretic four-step SCO behavior with the sequence of LS↔HS0.25LS0.75↔HS0.5LS0.5↔ HS0.75LS0.25↔HS is found in a three-dimensional (3D) Hofmann-type metal-organic framework (MOF), which is evidenced by magnetic, differential scanning calorimetry, and crystal data. Further experiments involving guest exchange leads to the first reversible modulation of four-, two-, and one-stepped SCO behaviors, which provides a new strategy for developing multi-step SCO materials. [ABSTRACT FROM AUTHOR]

Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] ( 1Dy Cpttt=1,2,4-tri( tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt)2Dy]+ ( 2Dy) as a salt of the non-coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [ 2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low-lying Kramers doublets correspond to a well-defined MJ value, with no significant mixing even in the higher doublets. [ABSTRACT FROM AUTHOR]

An extremely rare non-Kramers holmium(III) single-ion magnet (SIM) is reported to be stabilized in the pentagonal-bipyramidal geometry by a phosphine oxide with a high energy barrier of 237(4) cm−1. The suppression of the quantum tunneling of magnetization (QTM) at zero field and the hyperfine structures originating from field-induced QTMs can be observed even from the field-dependent alternating-current magnetic susceptibility in addition to single-crystal hysteresis loops. These dramatic dynamics were attributed to the combination of the favorable crystal-field environment and the hyperfine interactions arising from 165Ho ( I=7/2) with a natural abundance of 100 %. [ABSTRACT FROM AUTHOR]

Achieving selective C−H activation at a single and strategic site in the presence of multiple C−H bonds can provide a powerful and generally useful retrosynthetic disconnection. In this context, a directing group serves as a compass to guide the transition metal to C−H bonds by using distance and geometry as powerful recognition parameters to distinguish between proximal and distal C−H bonds. However, the installation and removal of directing groups is a practical drawback. To improve the utility of this approach, one can seek solutions in three directions: 1) Simplifying the directing group, 2) using common functional groups or protecting groups as directing groups, and 3) attaching the directing group to substrates via a transient covalent bond to render the directing group catalytic. This Review describes the rational development of an extremely simple and yet broadly applicable directing group for PdII, RhIII, and RuII catalysts, namely the N-methoxy amide (CONHOMe) moiety. Through collective efforts in the community, a wide range of C−H activation transformations using this type of simple directing group have been developed. [ABSTRACT FROM AUTHOR]

All-solid-state sodium batteries, using solid electrolyte and abundant sodium resources, show great promise for safe, low-cost, and large-scale energy storage applications. The exploration of novel solid electrolytes is critical for the room temperature operation of all-solid-state Na batteries. An ideal solid electrolyte must have high ionic conductivity, hold outstanding chemical and electrochemical stability, and employ low-cost synthetic methods. Achieving the combination of these properties is a grand challenge for the synthesis of sulfide-based solid electrolytes. Design of the solid electrolyte Na3SbS4 is described, realizing excellent air stability and an economic synthesis based on hard and soft acid and base (HSAB) theory. This new solid electrolyte also exhibits a remarkably high ionic conductivity of 1 mS cm−1 at 25 °C and ideal compatibility with a metallic sodium anode. [ABSTRACT FROM AUTHOR]

Blockade of the protein-protein interaction between the transmembrane protein programmed cell death protein 1 (PD-1) and its ligand PD-L1 has emerged as a promising immunotherapy for treating cancers. Using the technology of mirror-image phage display, we developed the first hydrolysis-resistant D-peptide antagonists to target the PD-1/PD-L1 pathway. The optimized compound DPPA-1 could bind PD-L1 at an affinity of 0.51 μ M in vitro. A blockade assay at the cellular level and tumor-bearing mice experiments indicated that DPPA-1 could also effectively disrupt the PD-1/PD-L1 interaction in vivo. Thus D-peptide antagonists may provide novel low-molecular-weight drug candidates for cancer immunotherapy. [ABSTRACT FROM AUTHOR]

A record anisotropy barrier (319 cm−1) for all d-f complexes was observed for a unique FeII-DyIII-FeII single-molecule magnet (SMM), which possesses two asymmetric and distorted FeII ions and one quasi- D5 h DyIII ion. The frozen magnetization of the DyIII ion leads to the decreased FeII relaxation rates evident in the Mössbauer spectrum. Ab initio calculations suggest that tunneling is interrupted effectively thanks to the exchange doublets. [ABSTRACT FROM AUTHOR]

Hyperfine interaction, isotope effect, magnetization dynamics, single-molecule magnets, super-hyperfine interaction Inside Cover: Magnetization Dynamics on Isotope-Isomorphic Holmium Single-Molecule Magnets (Angew. Keywords: hyperfine interaction; isotope effect; magnetization dynamics; single-molecule magnets; super-hyperfine interaction EN hyperfine interaction isotope effect magnetization dynamics single-molecule magnets super-hyperfine interaction 26870 26870 1 12/15/21 20211220 NES 211220 B Nuclear-spin driven relaxation b collaborating with the ligands in lanthanide single molecule magnets (SMMs) remains ambiguous. [Extracted from the article]