Lanthanide-mediated tuning of electronic and magnetic properties in heterotrimetallic cyclooctatetraenyl multidecker self-assemblies

The synthesis of a novel family of homoleptic COT-based heterotrimetallic self-assemblies bearing the formula [LnKCa(COT)₃(THF)₃] (Ln(iii) = Gd, Tb, Dy, Ho, Er, Tm, and Yb) is reported followed by their X-ray crystallographic and magnetic characterization. All crystals conform to the monoclinic P2₁/c space group with a slight compression of the unit cell from 3396.4(2) ų to 3373.2(4) ų along the series. All complexes exhibit a triple-decker structure having the Ln(iii) and K(i) ions sandwiched by three COT²⁻ ligands with an end-bound {Ca²⁺(THF)₃} moiety to form a non-linear (153.5°) arrangement of three different metals. The COT²⁻ ligands act in a η⁸-mode with respect to all metal centers. A detailed structural comparison of this unique set of heterotrimetallic complexes has revealed consistent trends along the series. From Gd to Yb, the Ln to ring-centroid distance decreases from 1.961(3) Å to 1.827(2) Å. In contrast, the separation of K(i) and Ca(ii) ions from the COT-centroid (2.443(3) and 1.914(3) Å, respectively) is not affected by the change of Ln(iii) ions. The magnetic property investigation of the [LnKCa(COT)₃(THF)₃] series (Ln(iii) = Gd, Tb, Dy, Ho, Er, and Tm) reveals that the Dy, Er, and Tm complexes display slow relaxation of their magnetization, in other words, single-molecule magnet (SMM) properties. This behaviour is dominated by thermally activated (Orbach-like) and quantum tunneling processes for [DyKCa(COT)₃(THF)₃] in contrast to [ErKCa(COT)₃(THF)₃], in which the thermally activated and Raman processes appear to be relevant. Details of the electronic structures and magnetic properties of these complexes are further clarified with the help of DFT and ab initio theoretical calculations.

A new class of heterotrimetallic COT-based self-assemblies accommodates metals from groups I–III in three different oxidation states and enables tuning of electronic and magnetic properties.     

Metal-free cascade boron-heteroatom addition and alkylation with diazo compounds

Transition metal-catalyzed carbene transfer reaction is one of the most notable advances for C-C bond formation reactionsduring the past decade,which has been widely employed in the preparation of C3-substituted indoles,Here,we described an efficient exa mple of catalyst-and metal-free aminobo ration of alkynes and C—C bond formation with diazo compounds to produce C3-substituted indoles,Diverse alkynyla nilines and diazo compounds ca n be utilized for this tandem transfo rmation under mild reaction conditions,re sulting in broad functional group co mpatibility.Additionally,this metal-free strategy can be extended to construct substituted benzofurans.     

Stress Relaxation Behaviors of Monocrystalline Silicon Coated with Amorphous SiO2 Film:A Molecular Dynamics Study

Long-lasting constant loading commonly exists in silicon-based microelectronic con-tact,as well as the chemical mechanical polishing area.In this work,the stres...     

Development of a Genus-Universal Nucleotide Signature for the Identification and Supervision of Ephedra-Containing Products

Ephedra plants generally contain ephedrine alkaloids, which are the critical precursor compounds of methamphetamine (METH). METH could cause serious physical and mental damage, and therefore Ephedra materials are strictly in supervision internationally. However, unlawful utilization of Ephedra herbs and its products still exist. Thus, it is imperative to establish a universal method for monitoring Ephedra ingredients in complex mixtures and processed products. In this study, 224 ITS2 sequences representing 59 taxa within Ephedra were collected, and a 23-bp genus-level nucleotide signature (GTCCGGTCCGCCTCGGCGGTGCG) was developed for the identification of the whole genus. The specific primers MH-1F/1R were designed, and 125 individuals of twelve Ephedra species/varieties were gathered for applicability verification of the nucleotide signature. Additionally, seven batches of Chinese patent medicines containing Ephedra herbs were used to test the application of the nucleotide signature in complex and highly processed materials. The results demonstrated that the 23-bp molecular marker was unique to Ephedra and conserved within the genus. It can be successfully utilized for the detection of Ephedra components in complex preparations and processed products with severe DNA degradation. The method developed in this study could undoubtedly serve as a strong support for the supervision of illegal circulation of Ephedra-containing products.     

Photocatalytic Carboxylation of Phenyl Halides with CO2 by Metal-Organic Frameworks Materials

In this work,important commercial pharmaceutical intermediates,phenylpropionic acid compounds,are successfully obtained by catalyzing the reaction of carbon dioxide with phenyl halides using MOF-5,a typical metal-organic framework(MOF)material.The influence of temperature,pressure,catalyst type and light on the reaction is investigated,and a 90.3%selectivity towards fluorophenylpropionic acid is reached.Significantly,the catalysts are effective for varied benzyl compounds containing different substituent groups.The catalysts are stable and remain active after three cycles.     

基于LabVIEW的超导磁体数采与测控系统研究

根据研制的大口径、高场强的超导强磁装置的特点,选择基于LabVIEW的数据采集和测控系统。低温传感器共六支,分别安装于磁体氦槽和冷屏不同位置,其中碳电阻温度计Cernox三支,铂电阻温度计Pt100两支、Pt1000一只,用于监测磁体温度;超导氦液面计一个,用于监测氦液面高度;根据磁体参数匹配研制了一套可调励磁速率的磁体专用直流电源及其失超保护系统,保证磁体安全运行。所有数据通过NI公司内插DAQ6251数据采集卡的PX I采集,用LabVIEW编写数据采集程序和人机界面。     

新型三段高性能的长波段掺铒光纤超荧光光源的研究

提出了一种第一段无泵浦、第二段前向泵浦和第三段后向泵浦的三段级联掺铒光纤超荧光光纤光源的新结构.数值分析了泵浦光波长、铒光纤长度以及泵浦比例对新结构性能的影响.结果表明可以找到一组适合制作成本低廉、输出功率高、谱平坦的长波段掺铒光纤超荧光光源.     

激光陀螺锁区特性的研究

从理论和试验两个方面,研究了四边形腔环行激光陀螺的锁区特性.利用环行腔中背向散射光束具有相干性,导出了环行谐振腔综合背向散射与反射镜、反射镜之间的相对位置的关系.在有两个位移反射镜的四边形谐振腔中,理论上得到了综合背向散射系数与谐振腔腔长具有双波长周期.利用综合背向光强实验及锁区与陀螺工作模数实验分别验证了理论的正确性.试验证实散射光的强度与谐振腔的工作模数存在双模周期性,综合背向散射系数大,陀螺锁区大,反之亦然.     

激光陀螺磁灵敏度特性研究

分析、计算了激光陀螺的磁灵敏度特性,并进行了磁灵敏度试验.试验结果及分析表明：在腔体加工准确度不变的情况下,采用合理的设计可以大大降低激光陀螺在某些方向上的磁灵敏度,同时磁试验结果对于设计激光陀螺的磁屏蔽结构具有一定的实用价值.