微调镝(Ⅲ)离子配位环境提升单离子磁体有效能垒

对于合成化学家来说,通过合成策略调控单离子磁体的磁动力学是一项艰巨的任务。我们以三（2-羟基亚苄基）三氨基胍配体（L）合成了2例单核Dy（Ⅲ）配合物[Dy（L）₂（H₂O）₂]ClO₄·2H₂O·2CH₃CN·CH₃OH（1）和[Dy（L）₂（H₂O）₂]CF₃SO₃·4H₂O·2CH₃OH（2）。对其结构和磁性研究表明,不同的抗衡阴离子对于配合物1和2的动态磁行为有显著影响。2个配合物中,Dy（Ⅲ）中心都具有三角形十二面体D_2d对称性,在零直流场下表现出单离子磁体的行为,其有效能垒分别为358 K（1）和309 K（2）。结构参数对比表明轴向位置的键长和键角微小变化对轴向配体场产生了显著的影响,而轴向配体场的微小变化导致了2个配合物交流磁性的差异。     

一维和二维镝(Ⅲ)配合物的慢磁弛豫

分别用稀土醋酸盐和稀土高氯酸盐与希弗碱配体和巯基烟酸配体反应得到了两例镝配合物[Dy₂(OAc)₆H₂O]_n(1)和{[DyL(H₂O)₄]ClO₄·H₂O}_n(2)(L=2,2'-二硫代-二(3-吡啶甲酸)),并通过单晶X-射线衍射、元素分析、红外光谱和磁性测试对其进行了表征。结构研究和磁性测试表明:化合物1是羧基桥连的一维链结构,该化合物表现出慢磁弛豫性质,有效能垒为2 K;化合物2是通过原位生成的二硫键桥连的二维网状结构,表现出明显的铁磁相互作用和慢磁弛豫行为。     

双层金属纳米光栅的TE偏振光异常透射特性

根据在亚波长金属光栅表面添加电介质会引起TE偏振光的透射异常性, 应用严格耦合波理论和时域有限差分方法, 研究了双层金属纳米光栅在TE偏振光入射时产生的异常透射现象. 利用等效折射率方法建立了双层金属光栅的等效模型, 得到了TE偏振光透射率与聚合物的折射率、厚度以及金属层厚度的变化关系. 确认了结构中聚合物是透射异常出现的必要条件, TE偏振光以波导电磁模式在其中传播, 并认为类Fabry-Perot腔谐振是透射峰值产生的主要原因.     

Spin topology and ferromagnetic coupling: synthesis and magnetic properties of [CuII3CrIII] tetranuclear complexes of [14]N4 macrocyclic oxamides

Three novel tetranuclear macrocyclic complexes, [(CuL¹)₃Cr](ClO₄)₃·3H₂O (1), [(CuL²)₃Cr](ClO₄)₃·3H₂O (2) and [(CuL³)₃Cr](ClO₄)₃·3H₂O (3) [L¹, L² and L³ are the dianions of three [14]N₄ and [15]N₄ macrocyclic oxamides, namely 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene,2,3-dioxo-5,6:13,14-dibenzo-9-methyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene and 2,3-dioxo-5,6:14,15-dibenzo-7,13-bis(ethoxycarbonyl)-1,4,8,12-tetraazacyclotetradeca-7,12-diene, respectively], have been prepared and characterized. These complexes are the first examples of Cu₃Cr species exhibiting spin topology with all the spins parallel in the ground state. Cryomagnetic studies on (1) (2–300 K) and (3) (77–300 K) revealed that the Cu^II and Cr^III ions interact ferromagnetically through the oxamido bridge, with the exchange integral J = 6.7 cm^–1 for (1) and J = 6.3 cm^–1 for (3) based on = –2J _{i j} . The ferromagnetic interaction has been rationalized in terms of strict orthogonality of the magnetic orbitals. The oxamido bridge is also more efficient than the oxalato bridge at propagating the ferromagnetic interaction.     

三维氢键超分子化合物[H3cth][Fe(CN)6]·3H2O的合成与结构

用内消旋５，７，７，１２，１４，１４－六甲基－１，４，８，１１－四氮杂环十四烷（ｃｔｈ）和Ｋ_３［Ｆｅ（ＣＮ）_６〕合成了氢键连接的超分子化合物［Ｈ_３ｃｔｈ］［Ｆｅ（ＣＮ）_３］·３Ｈ_２Ｏ．该化合物的晶体属三斜晶系，Ｐ－１空间群，晶胞参数ａ＝０．９３０ ９７（９）ｎｍ，ｂ＝１．０５１ ６０（１１）ｎｍ，ｃ＝１．６３８ ４７（１７）ｎｍ，ａ＝１０１．０７７（２）°，β＝９０．８６０（２）°，γ＝１１１．６７１（２）°， Ｖ＝１．４５６ ４（３） ｎｍ３， Ｚ＝２， Ｒ＝０．０４１５．晶体中质子化的大环四胺与六氰合铁（Ⅱ ）离子之间通过氢键连接成二维层状结构，而水分子所形成的氢键使化合物呈现三维超分子网络．     

Air-stable High Performance Macrocyclic Dysprosium (Ⅲ) Single-Ion Magnet北大核心CSCD

Designing and preparing air-stable high-performance single-molecule magnets (SMMs) is of great significance toward the implementation of SMMs in high-density information storage,quantum computation and molecular-based spintronics devices. Herein,an air-stable macrocyclic Dy (III) single-ion magnet with pentagonal bipyramidal local symmetry is obtained by the reaction between N,N'-bis (2-aminoethyl)-1,3-propanediamine and 2,6-diacetylpyridine with the dysprosium ion as template. Single crystal X-ray diffraction reveals that the dysprosium ion is encapsulated in the equatorial plane with BPh4− as counter anion and the axial position is occupied by two Ph3 SiO−. The state magnetic measurements gives the χM T value of 13. 96 cm3·K/mol at room temperature,close to the theoretical value of 14. 17 cm3·K/mol for one isolated Dy (III) ion. The dynamic magnetic measurements confirm its typical SMM behavior under a zero dc field with the effective magnetic reversal barrier up to 1008 K. Magneto-structural investigations show that the excellent SMM properties are attributed to the D5h local symmetry and the strongly axial crystal field created by two Ph3 SiO− for the dysprosium ion. Thermogravimetric analysis indicates that the compound is extremely air stable and the decomposition temperature reaches up to 297 ℃ ,which provides a promising avenue for depositing high performance SMMs on conductive substrate surfaces. © 2022, Science Press (China). All rights reserved.     

ZnO电子结构和p型传导特性的第一性原理研究

基于密度泛函理论(DFT)框架下的第一性原理平面波超软赝势方法(USPP)，对不同掺杂情况的ZnO晶体几何结构分别进行了优化计算，从理论上给出了ZnO的晶胞参数，得到了ZnO的总体态密度(TDOS)和氮原子2p态的分波态密度(PDOS).计算结果表明：原胞体积随着掺杂比例的提高而逐渐减小；将氮铝按照2∶1的原子比例共掺可以使氮的掺杂浓度比只掺杂氮时明显提高，且随着铝在锌靶中掺入比例的增加，载流子迁移率提高，浓度增大，使得p型ZnO电导率提高，传导特性增强. 关键词： 共掺 p型传导 态密度 第一性原理     

掺硼水吸附碳纳米管电子场发射性能的第一性原理研究

运用第一性原理研究了掺硼碳纳米管(BCNT)顶端吸附水分子后的电子场发射性能.结果表明：掺B及吸附H₂O的碳纳米管(BCNT+H₂O)端部形成电子聚集的原子尺度微区,其电子态密度(DOS)在费米能级(E_f)附近有很大提高.根据计算的电子DOS,HOMO/LUMO及Mulliken电荷分布等可知BCNT+H₂O比CNT+H₂O有更好的场发射性能. 关键词： 掺硼碳纳米管 吸附 密度泛函理论 电子场发射     

Synthesis and structural characterization of a novel tricobalt cluster with 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol

A novel chelating bisoxime ligand, 4,4′-dichloro-2,2′-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol (H₂L), and its corresponding trinuclear Co(II) cluster {[CoL(C₂H₅OH)]₂(OAc)₂Co} · 2C₂H₅OH (1) have been synthesized and characterized by elemental analyses, IR, ¹H NMR, TG-DTA and X-ray diffraction methods. The Co(II) cluster crystallizes in the triclinic system, space group P ? 1 with cell dimensions a = 9.412(2) Å, b = 11.868(2) Å, c = 14.280(2) Å, α = 108.131(3)°, β = 108.924(3)°, γ = 97.909(2)°, V = 1382.6(4) Å³, Z = 1, R ₁ = 0.0790, wR ₂ = 0.1869. In the Co(II) cluster, there are two ligand moieties (which provide N₂O₂ donors), two acetate ions and two ethanol molecules, which result in the formation of three slightly distorted octahedral geometries around the Co(II) ions.     

圆二色谱研究两个新的呋喃雅槛蓝型倍半萜的绝对构型

前文我们从长梗千里光(Senecio Kaschkarovii)和森林千里光(Senecio Nernenrisis)中分离得到3个10位是羟基的9-氧-呋喃型倍半萜(Ⅰ—Ⅳ),其中Ⅰ和Ⅳ为首次发现的新化合物。这3种化合物A、B环是顺式连接,而6位取代基是β构型,这仅仅是通过它们的核磁共振氢谱与类似化合物对照及NOE差谱确定的。由于此类化合物10位缺少氢,使得用核磁共振氢谱确定A、B环的连接方式尚显论据不足。为进一步证明我们前文的推断的正确性,本文制备