Synthesis and magnetic properties of the novel dithiadiazolyl radical, p-NCC6F4C6F4CNSSN*

The dithiadiazolyl radical p-NCC6F4C6F4CNSSN* (4) retains its monomeric nature in the solid state with molecules linked together into chains via supramolecular CN-S interactions. Variable temperature magnetic studies on 4 show that it behaves as a near-ideal Curie paramagnet (|theta| less than 0.1 K), indicating negligible intermolecular exchange. The effective magnetic moment (1.78 micro(B)) is temperature independent and in excellent agreement with the value expected for an S = 1/2 paramagnet with g = 2.01(1.74 micro(B)). The lack of exchange coupling between radicals is attributed to the absence of significant orbital overlap between radical centres.     

Ab initio STUDIES ON NITROXYL RADICAL MODELS OF ORGANIC FERROMAGNETS

The magnetic coupling between the unpaired spin of nitroxyl group (>N--O) and itsneighbor sp~2 carbon atom has been studied in detail by UHF/6--31G and MP4/6-31G methods.and a number of conjugate nitroxyl diradicals have also been studied by ab initio UHFmethod. A simple topological rule about the ferromagnetic coupling between two nitroxylgroups has been revealed by our calculation. Based on this rule as well as ab initio cal-culation, some nitroxyl radical models of organic ferromagnets (OFM) have been proposed,and the possible way of synthesis has also been suggested. Moreover, the ab initio UHF-crystal orbital (UHF--CO) method has been used to characterize the electronic band struc-ture of one of the models. The ab initio UHF--CO results show that this model is a verypromising candidate of OFM,     

Studying the Origin of the Antiferromagnetic to Spin‐Canting Transition in the β‐p‐NCC6F4CNSSN. Molecular Magnet

The crystal structure of the spin‐canted antiferromagnet β‐p‐NCC₆F₄CNSSN^. at 12 K (reported in this work) was found to adopt the same orthorhombic space group as that previously determined at 160 K. The change in the magnetic properties of these two crystal structures has been rigorously studied by applying a first‐principles bottom‐up procedure above and below the magnetic transition temperature (36 K). Calculations of the magnetic exchange pathways on the 160 K structure reveal only one significant exchange coupling (J(d1)=?33.8 cm^?1), which generates a three‐dimensional diamond‐like magnetic topology within the crystal. The computed magnetic susceptibility, χ(T), which was determined by using this magnetic topology, quantitatively reproduces the experimental features observed above 36 K. Owing to the anisotropic contraction of the crystal lattice, both the geometry of the intermolecular contacts at 12 K and the microscopic J_AB radical–radical magnetic interactions change: the J(d1) radical–radical interaction becomes even more antiferromagnetic (?43.2 cm^?1) and two additional ferromagnetic interactions appear (+7.6 and +7.3 cm^?1). Consequently, the magnetic topologies of the 12 and 160 K structures differ: the 12 K magnetic topology exhibits two ferromagnetic sublattices that are antiferromagnetically coupled. The χ(T) curve, computed below 36 K at the limit of zero magnetic field by using the 12 K magnetic topology, reproduces the shape of the residual magnetic susceptibility (having subtracted the contribution to the magnetization arising from spin canting). The evolution of these two ferromagnetic J_AB contributions explains the change in the slope of the residual magnetic susceptibility in the low‐temperature region.     

极性转换在有机合成中的应用

本文主要论述极性转换的基本概念和它在有机合成中的作用。先介绍了羰基化合物(醛、酮)的极性转换的各种方法,然后谈到胺的极性转换方法和最常用的极性转换试剂。     

元素有机化合物在合成应用中的发展

本文回顾了元素有机化合物在有机合成中应用的发展史。分别叙述两位诺贝尔奖金获得者,Brown和Wittig,以及Vollhardt和野依良治成功的经历。对元素有机化学应用于有机合成作了展望。     

有机成分标准物质的研究

列出了国家标准物质研究中心最近研制的有机成分标准物质。高纯度、定值准确可靠、良好的溯源性和系列性是这些标准物质的特点。对其应用作了介绍,并指出了将来的研究方向。     

Robust S4⋅⋅⋅O Supramolecular Synthons: Structures of Radical-Radical Cocrystals [p-XC6F4CNSSN]2[TEMPO] (X=F,Cl, Br,I, CN)

Cocrystallization of the dithiadiazolyl (DTDA) radicals p-XC₆F₄CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [p-XC₆F₄CNSSN]₂[TEMPO] ( 1 – 5 ) whose structures all reflect a common S₄⋅⋅⋅O supramolecular motif. The nature of this interaction was probed by DFT calculations (M06/aug-cc-pVDZ) on 1 which revealed that the enthalpy of formation of the [C₆F₅CNSSN]₂[TEMPO] supramolecular motif from [C₆F₅CNSSN]₂ and TEMPO is substantial (−54.0 kJ mol⁻¹). Electronic structure calculations revealed a TEMPO-based doublet S= configuration as the ground state with limited spin density on the DTDA rings (2.4 %). The corresponding spin quartet state is +78.9 kJ mol⁻¹ higher in energy. An atoms-in-molecules analysis reveals four bond critical points (BCPs) between the TEMPO O and the DTDA S atoms as well as additional BCPs between selected DTDA S atoms and methyl H atoms of the TEMPO molecule. Herein, the structures of 2 – 5 are considered within the context of a hierarchical view of competing and complementary intermolecular interactions; in particular, the established supramolecular CN⋅⋅⋅S−S synthon is sacrificed in order to form the new S₄⋅⋅⋅O interaction.     

有机小分子电致发光研究进展

有机电致发光具有发光亮度和发光效率高,材料易加工等传统的无机和液晶显示材料无可比拟的优点,并且可以通过改变分子结构或掺杂调谐发光的颜色.本文评述了近年来有机小分子电致发光材料的研究进展,简要介绍了有机电致发光的原理及其广阔的应用前景.     

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF THE ASYMMETRIC DITHIADIAZENE BrC6F4NSNSC6H4NO2

The asymmetric dithiadiazene BrC₆F₄NSNSC₆H₄NO₂ crystallizes in the space group P-1 and exhibits a 1D polar chain structure linked via structure-directing Br···O₂N synthons.     

有机元素分析中影响燃烧过程的因素

燃烧过程是有机元素分析中十分重要而又较难把握的一个步骤。本文介绍了有机元素分析中影响燃烧过程的因素及控制方法。     

Study of the ionic conductivity of Ca6La4(PO4)2(SiO4)4F2 and Ca4La6(SiO4)6F2

In order to enhance our knowledge about the Ca_10−xLa_x(PO₄)_6−x(SiO₄)_xF₂ (0 ≤ x ≤ 6) series, whose chemical stability decreases as the substitution degree increases, Ca₆La₄(PO₄)₂(SiO₄)₄F₂ and Ca₄La₆(SiO₄)₆F₂ compounds were prepared through a solid-state reaction. Their ionic conductivity was measured by impedance spectroscopy. The results indicate that the conductivity increases with substitution, and fits the Arrhenius equation over the investigated temperature range. At high temperatures, a change in the activation energy has been observed, which has been related to the nature of the Ca/La–F bond, i.e. to the polarizability of lanthanum.     

煤中黄铁矿及其毗邻的有机硫

用透射电镜及扫描电镜考察了煤中黄铁矿颗粒及其毗邻的有机硫含量。结果表明,与黄铁矿毗邻的有机硫分布均匀;在煤的热解过程中,黄铁矿(FeS_2)可能转化为磁黄铁矿(Fe_(1-x)S)或磁铁矿(Fe_3O_4),而部分无机硫则扩散到附近煤体中。测试在距黄铁矿颗粒边缘1—40/μm范围的媒体中进行。热解温度范围多数情况下为400—550℃。     

磷试剂在有机合成中的应用

含磷试剂在有机合成领域中的应用主要在于形成碳碳双键,官能团转换,脱氧及还原作用,活性基团载体,催化作用。不论是在常见的Witting反应,还是磷磷化氯基酸自身催化成肽作用中,磷试剂都发挥着重要的作用。     

有机物燃烧热测定方法的改进

对有机物燃烧热的测定方法进行了改进。改变点火丝的安装方法,采用高性能量热计,改变氧弹内氧气的压力及燃烧样品的用量,确定了新的测定方法。采用新的测定方法测定萘的燃烧热,测定结果的相对误差为0．05％,相对标准偏差为0．077％。     

有机羧酸的光催化分解反应

测定了各种有机羧酸在Pt/TiO₂粉末悬浮体系中的光催化分解速度。不同分子结构的有机羧酸的光催化分解速度有明显的差别。通过计算与羧基相连的各种基团的诱导效应指数,发现基团的推电子能力对有机羧酸的光催化分解速度起主导作用,找到了有机羧酸光催化分解速度与其分子结构间的关系。