From geometric to charge-distribution symmetry:deeper insights into lifting the performance of dysprosium single-ion magnets

Crystal-field symmetry of lanthanide ions plays a critical role in suppressing quantum tunneling of magnetization(QTM)in single-molecule magnets(SMMs),but high-performance SMM design and modulation remain challenging only in view of the geometric symmetry of the first coordination sphere.Herein,two bis(semicarbazone)/bis(thiosemicarbazone)dysprosium singleion magnets with pentagonal bipyramid geometry were reported,and bis(thiosemicarbazone)lanthanide complexes have never been reported to the best of our knowledge.They served as good archetypes to study the magneto-structural relationships based on the charge distribution.The complex with more ideal geometric symmetry displays fast zero-field QTM with negligible“effective barrier”,owing to the defective charge distribution.By modulating the transverse crystal field via the replacement of the O sites with the less charged and larger radius S atoms,it results in lower geometric but higher charge-distribution symmetry,giving rise to the significant suppression of QTM and the enhancement of reversal barrier up to ca.1,000 K.These results demonstrate that the charge-distribution symmetry can be chemically tailored by modification of the crystal field,which is essential for designing high-performance SMMs.

Microstructure and properties of honeycomb composite films containing Eu and Sn

Honeycomb composite films were prepared by breath figure method via a straightforward,one-step process by doping complex containing Eu or Sn into polystyrene-b-poly(acrylic acid) solution.Several key influencing factors,such as the concentration of the block polymer solution,the relative humidity of the environment and the amount of complexes,were investigated to control micropore size and tune film surface properties.The characteristics of the composite films were studied by scanning electron microscopy(SEM),atomic force microscopy(AFM),X-ray diffraction(XRD),ultraviolet and emission spectra.Results indicate that composite films containing Eu have excellent optical performance,and micro-patterned bowl-like SnO_(2) microparticles could be fabricated from composite films containing Sn after being calcined at 600℃ for 5 h.This general approach for the fabrication of honeycomb composite films opens a convenient and effective route to the functional modification of honeycomb films and offers new prospects for the application in miniaturized sensors,micro-reactor and catalysis.

Competitive role of film-like austenite and transition carbides on hydrogen embrittlement resistance and impact toughness in bainite-containing quenched and partitioned steel

A microstructure composed of martensite matrix,lower bainite,and stable film-like austenite was designed by a quenching and isothermal bainitic holding process in a 0.30C–2.69Mn–1.71Si(wt.%)steel.The yield strength,tensile strength,and ductile-to-brittle transition temperature(DBTT)of the high-strength steel thus obtained were 1263 MPa,1521 MPa,and-33℃,respectively,and at-20℃,it showed superior low-temperature toughness,which reached 77.5 J/cm^(2).Meanwhile,it showed excellent hydrogen embrittlement(HE)resistance,and the total elongation loss is only 3.1%after 15 min of hydrogen charging.The excellent comprehensive performance is attributed to the fact that fine stable austenite with film-like morphology hindered the crack nucleation and propagation,and hindered hydrogen diffusion as a hydrogen trap.However,with a decrease in the isothermal temperature,transition carbide precipitation was accompanied by a further decrease in austenite grain size.For this condition,although transition carbides can act as effective hydrogen traps,excessive precipitation decreased the carbon content of retained austenite and increased the deformation heterogeneity between austenite and martensite matrix,leading to weakened austenite stability and HE resistance,a total elongation loss of approximately 39%(15 min hydrogen charging),a sharp decrease in impact toughness,and an increase in DBTT.The competitive role of film-like austenite and transition carbides on the comprehensive mechanical performance of steel is revealed,especially the suppression of crack nucleation and propagation that will provide a guide for the design of high strength steels with excellent impact toughness and HE resistance.

Preparation of luminescent polystyrene microspheres via surface-modified route with rare earth(Eu^(3+) and Tb^(3+))complexes linked to 2,2'-bipyridine

Luminescent polystyrene microspheres were easily fabricated from poly(styrene-co-methacrylic acid)and aqueous RE(III) chloride solution(RE=Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative charges of carboxyl groups on the surface of microspheres coordinated with rare earth ions at first, such as complexes covalently linked to 2,20-bipyridine, resulting in strong photoluminescence. Various methods, including transmission electron microscope(TEM), scanning electron microscope(SEM), energy dispersive spectroscopy(EDS),Fourier transform infrared spectroscopy(FT-IR), and fluorescence spectrophotometer, were used to characterize the resultant polystyrene composite microspheres. This work highlights the idea that it is facile to synthesis luminescent microspheres by surface-modified method directly.

Synthesis and microwave absorbing properties of La-doped Sr-hexaferrite nanopowders via sol-gel auto-combustion method

La-doped Sr-hexaferrite（Sr（1-x）LaxFe（12）O（19））（x=0.05,0.10,0.15,0.20） nanopowders with particle size ranging from 80 to 110 nm were successfully synthesized by sol-gel auto-combustion. The phase formation temperature increases, while the particle size decreases as the Ladoping content goes up. The partial substitution of Sr^（2＋） by La^（3＋） results in the suppression effects on the growth-up of the crystallites and the enhancement of the electron hopping between Fe^（3＋） with different valences, which leads to the improvement in the dielectric loss and magnetic loss.Therefore, both the microwave absorbing abilities and absorbing frequency ranges are tuned by La-doping. The synthesized Sr-hexaferrite nanopowders with doping element content of 0.10 demonstrate the fine broad microwave absorbing properties.

Enhancing single-molecule magnet behavior of linear Co~Ⅱ-Dy~Ⅲ-Co~Ⅱ complex by introducing bulky diamagnetic moiety

Single-molecule magnets(SMMs)are regarded as promising candidates for ultrahigh-density storage,quantum information processing and molecular spintronics.It is a crucial challenge for chemists to modulate magnetic dynamics of SMMs.Here,we successfully synthesized two 3d-4f polynuclear compounds[Co_2Dy(TTTT^(Cl))_2(MeOH)]NO_3·3MeOH(1)and[Co_2Dy(TTTT^(Cl))_2(MeOH)][Co(HTTTT^(Cl))](NO_3)_2·2.5MeOH·2H_2O(2),where H_3TTTT^(Cl)=2,2′,2′′-(((nitrilotris(ethane-2,1-diyl))tris(azanediyl))tris(methylene))tris-(4-chlorophenol).On applying the approach by co-crystallization of bulky diamagnetic moiety,the effective energy barrier enhances from 401 K(1)to 536 K(2),which are both among the highest d-f heterometallic SMMs.

Synthesis of novel hydrated ferric oxide biochar nanohybrids for efficient arsenic removal from wastewater

Hydrated ferric oxide(HFO)has high adsorption efficiency for As(Ⅲ).However,its high self-aggregation usually reduces the efficiency and limits the scaledup application.Herein,biochar(BC),with large surface area and amounts of surface functional groups was used to tune the loading and distribution of HFO to prepare an efficient adsorbent(HFO/BC)via in-situ synthesis method.The influence of the mass ratio of iron salt to BC on HFO/BC morphology was investigated,and the mechanism was discussed.The results showed that novel HFO was formed and distributed uniformly on the surface of BC when the mass ratio of iron salt to BC was 5:1.The adsorption kinetics and isotherms studies show that the novel HFO/BC(5:1)composite can fast treat As(Ⅲ)with a high adsorption capacity of 104.55 mg·g^(-1),indicating that it is a potential material for removing arsenic from polluted water.

Preparation of flexible rubber composites with high contents of tungsten powders for gamma radiation shielding

To prepare tungsten/rubber composites with good gamma-ray shielding performances and fine mechanical properties,a composite surface modifier is employed to make surface modification of the tungsten powders.

Synthesis and properties of strontium hexa-ferrite ultrafine powders via a CTAB-assisted co-precipitation method

Single-phase SrM ultrafine powders with single-domain particle ranging from 200 to 400 nm in size were successfully synthesized by a cetyltrimethylammonium bromide（CTAB）-as sis ted co-precipitation method,and excellent magnetic properties with saturation magnetization of 68.6 A·m^2·kg^（-1） and coercive field of 0.5250 T are obtained.As CTAB content exceeds 5.0 wt%,the impurities emerge due to the deterioration of simultaneous precipitations of the starting materials and the deviation of Sr/Fe molar ratio from stoichiometry ratio in the local microdomains by employing CTAB in co-precipitation process.Also,the use of CTAB can effectively improve the homogeneities of Fe-precursor particles with Sr-precursor particles,exert surface barriers to inhibit interdiffusion,and constrain the crystal growth in the local microdomains during sintering,resulting in smaller particle sizes and more uniform particle size distribution.

Design and properties of calcium copper titanate/poly(dimethyl siloxane) dielectric elastomer composites

The high phase content of inorganic dielectric fillings will give a strong electric driving force and hard matrix. That is a contradiction in enhancing the electrodeformation of dielectric elastomers(DEs). Therefore, in this paper, by focusing on how to approach a balance between these and finding an effective way to tune the electric response of the DEs, the theoretical calculation and experimental investigation based on calcium copper titanate(CCTO)/poly(dimethyl siloxane)(PDMS) were carried out. It is found that CCTO with a smaller particle size shows a larger dielectric parameter. With smaller CCTO particle as the fillings, the fabricated elastomer composite would approach to a low modulus by a proper CCTO phase morphology in the matrix.

Seeking magneto-structural correlations in easily tailored pentagonal bipyramid Dy (Ⅲ) single-ion magnets

Controlling molecular magnetic anisotropy via structural engineering is delicate and fascinating,especially for single-molecule magnets(SMMs).Herein a family of dysprosium single-ion magnets(SIMs)sitting in pentagonal bipyramid geometry have been synthesized with the variable-size terminal ligands and counter anions,through which the subtle coordination geometry of Dy(Ⅲ)can be finely tuned based on the size effect.The effective energy barrier(Ueff)successfully increases from 439 to 632 K and the magnetic hysteresis temperature(under a 200 Oe/s sweep rate)raises from 11 to 24 K.Based on the crystal-field theory,a semi-quantitative magneto-structural correlation deduced experimentally for the first time is revealed that the Ueff is linearly proportional to the structural-related value S20 corresponding to the axial coordination bond lengths and the bond angles.Through the evaluation of the remanent magnetization from hysteresis,quantum tunneling of magnetization(QTM)is found to exhibit negative correlation with the structural-related value Stun corresponding to the axial coordination bond angles.