Light- and temperature-assisted spin state annealing: accessing the hidden multistability

Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.

Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂], revealing the hidden multistability of spin states.     

不同夹带剂对3种丹参酮超临界CO2流体萃取效果的影响

使用不同夹带剂,用超临界CO₂流体萃取丹参中3种丹参酮,研究不同夹带剂的萃取效果。在优化操作条件下萃取丹参中3种丹参酮,HPLC测定萃取物中3种丹参酮的质量分数。3种夹带剂中,95%（V/V）极性物质乙醇效果最好,其次为丙酮、正辛烷。用超临界CO₂流体萃取丹参中3种丹参酮,为了提高萃取率,须使用极性溶剂乙醇作为夹带剂。     

基于曲线问题情境的信息化教学尝试*——以“沉淀溶解平衡”为例

基于高中生对实验曲线理解困难的现状,为挖掘实验曲线的教学价值,以沉淀溶解平衡为例,结合课堂演示实验和教学软件,设计了“宏观微观符号曲线”多重表征教学为一体的实验探究课。根据沉淀溶解平衡实验证据,绘制实验曲线,构建微观模型和图像,从而培养学生的证据收集与应用意识,提高学生对曲线的分析和理解能力,领会各种变化曲线的来源。在曲线理解的基础上建立“溶解平衡转化”思维模型,以此为开展“曲线融入式”的问题引导型实验教学提供参考案例。     

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

Science China Chemistry - Controlling molecular magnetic anisotropy via structural engineering is delicate and fascinating, especially for single-molecule magnets (SMMs). Herein a family of...     

Enhancing single-molecule magnet behavior of linear Co<Superscript>II</Superscript>-Dy<Superscript>III</Superscript>Co<Superscript>II</Superscript> 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 [Co₂Dy(TTTT^Cl)₂(MeOH)]NO₃·3MeOH (1) and [Co₂Dy(TTTT^Cl)₂ (MeOH)][Co(HTTTT^Cl)](NO₃)₂·2.5MeOH·2H₂O (2), where H₃TTTT^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.     

结晶水对硫酸铜与丁腈橡胶之间配位交联反应的影响

利用动态力学分析(DMA)、差示扫描量热分析(DSC)、扫描电子显微镜(SEM)、平衡溶胀法、力学性能测试等分析手段, 通过研究五水硫酸铜(CuSO4·5H2O)填充的NBR考察了结晶水对CuSO4与NBR之间配位交联反应的影响. 结果表明, 结晶水的存在可以促进该配位交联反应.     

Linear dependence of the intensity of the [M + H]+ ion peak in fast atom bombardment mass spectrometry on the basicity of meso-substituted octaethylporphyrins

A fast atom bombardment mass spectrometric study of the meso-substituent effect of Octaethylporphyrins (OEPX, X = NH₂, CH₃, H, CHO, Cl, CN, NO₂) is reported. The intensity of the [M + H]⁺ ion peaks was estimated quantitatively using an external standard, which was observed to be correlated linearly with the basicity (pK₃) of the OEPX. The pK₃ value of the OEPXs was obtained by titration with perchloric acid and it was observed to be correlated linearly with Hammett's σ_p value, with a ρ value of 1.38.     

汉墓女尸的外周神经与骨骼肌的显微与亚显微结构研究

本文报道了对一具二千一百年前埋葬于湖南长沙马王堆一号汉墓的女尸的外周神经和骨骼肌的显微和亚显微结构的研究,发现该古尸的外周神经和骨骼肌内的结缔组织纤维成份保存均较好,在电子显微镜下见到了胶原纤维典型的周期性带状结构,在腰丛神经纤维里,可看到轴索与交性的髓鞘,在一些保存较好的神经纤维中,髓鞘与轴索结构界限分明,腰大肌中有的肌纤维横纹很明显,腰丛神经中有残留的血管,但只保留了管壁的结缔组织,在此两种组织中均见到了细菌的芽孢。     

Reversible on-off switching of spin-crossover behavior via photochemical [2+2] cycloaddition reaction

Herein,we report the first example showing the reversible on-off switching of spin-crossover(SCO)property by solid state photochemical[2+2]reaction.The ultraviolet(UV)light-induced[2+2]cycloaddition reaction of 3-spy ligands in a twodimensional(2D)Hofmann-type framework[Fe(3-spy)₂{Pd(CN)₄}](1,3-spy=3-styrylpyridine),which shows a hysteretic twostep SCO behavior,gives a 3D Hofmann-type framework[Fe(rctt-3-ppcb){Pd(CN)₄}](2,rctt-3-ppcb=rctt-1,3-bis(3-pyridyl)-2,4-bis(phenyl)cyclobutane,r=reference group,c=cis and t=trans)accompanied with the disappearing of SCO properties.Moreover,upon heating at 250℃ for 12 h,the rctt-3-ppcb ligand in 2 could be partially dedimerized to 3-spy with 68%completion through single-crystal-to-single-crystal(SCSC)transformation,giving the annealing complexes[Fe(3-spy)1.36(rctt-3-ppcb)0.32{Pd(CN)₄}](3)which display an incomplete SCO behavior.The 2■3 interconversion is successfully achieved via continuous UV irradiation and thermal annealing,demonstrating the effectiveness of photochemical[2+2]reaction on switching on-off SCO properties.     

Nanoparticle Dispersion and Glass Transition Behavior of Polyimide-grafted Silica Nanocomposites

How to control the spatial distribution of nanoparticles to meet different performance requirements is a constant challenge in the field of polymer nanocomposites.Current studies have been focused on the flexible polymer chain systems.In this study,the rigid polyimide(PI) chain grafted silica particles with different grafting chain lengths and grafting densities were prepared by "grafting to" method,and the influence of polymerization degree of grafted chains(N),matrix chains(P),and grafting density(a) on the spatial distribution of nanoparticles in the PI matrix was explored.The glass transition temperature(Tg) of PI composites was systematically investigated as well.The results show that silica particles are well dispersed in polyamic acid composite systems,while aggregation and small clusters appear in PI nanocomposites after thermal imidization.Besides,the particle size has no impact on the spatial distribution of nanoparticles.When σ·N0.5<<(N/P)2,the grafted and matrix chains interpenetrate,and the frictional resistance of the segment increases,resulting in restricted relaxation kinetics and Tg increase of the PI composite system.In addition,smaller particle size and longer grafted chains are beneficial to improving Tg of composites These results are all propitious to complete the microstructure control theory of nanocomposites and make a theoretical foundation for the high performance and multi-function of PI nanocomposites.