Imidazole Coordinated Sandwich-type Antimony Polyoxotungstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ）

The imidazole covalently coordinated sandwich-type heteropolymngstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ） were obtained by the reaction of Na2WO4·2H2O, SbCl3·6H2O, NiCl2·6H2O [MnSO4·H2O, Co（NO3）2·6H2O, ZnSO4·7H2O] and imidazole at pH≈7.5. The structure of Na9[{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2]·32H2O was determined by single crystal X-ray diffraction. Polyanion [{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2}3]^9- has approximate C3v symmetry, imidazole coordinated six-nuclear duster [{Na（H2O）2}3{Ni（C3H4N2）}3]^9＋ is encapsulated between two （α-SbW9O33）^9-, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals （Na-Ni-Na-Ni-Na-Ni） in the central belt, and x-stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60%. The compounds were also characterized by IR, UV-Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

Effect of heat treatment on electronic phase in underdoped La2-xSrxCuO4 single crystal

Superconducting La1.937Sr0.063CuO4 crystals grown by the travelling-solvent floating-zone technique were thermally treated under various temperatures and oxygen pressures for moderately adjusting the oxygen content. The response of intrinsic electronic property of the crystals to the change of hole density in La2-xSrxCuO4 in the vicinity of the magic doping of x= 1/16 （= 0.0625） is studied in detail by magnetic measurements under various fields up to 1 T. It is found that when the superconducting critical temperature （Tc） increases with the oxygen content, there appears also a new subtle electronic state that can be detected from the differential curves of diamagnetic susceptibility dx/dT of the crystal sample. In contrast with the intrinsic state, the new subtle electronic state is very fragile under the magnetic fields. Our results indicate that a moderate change in oxygen doping does not significantly modify the intrinsic electronic state originally existing at the magic doping level.     

The effects of interstitial oxygen on superconducting electronic phases in strontium and oxygen co-doped La1.937Sr0.063CuO4＋δ

Strontium and oxygen co-doped La1.937Sr0.063CuO4＋δ superconductor with Tc≈ 40K, which is obtained by oxidizing strontium-doped starting ceramic sample La1.937Sr0.063CuO4 in NaC10 solution, is annealed under different conditions to allow interstitial oxygen to redistribute. The evolution of the intrinsic superconducting property with the oxygen redistribution is studied in detail by magnetic measurements in various fields. It is found that there occurs the electronic phase separation from the single superconducting phase with Tc ≈ 40 K into two coexisting superconducting states with values of Tc： 15 and 40K or of 15 and 35 K in this system, depending on annealing condition. Our results indicate that the 15, 35 and 40 K superconducting phases associated with the excess oxygen redistribution are all thermodynamically meta-stable intrinsic states in this Sr/O co-doped cuprate.     

一个新的夹心型杂多钨酸盐Na6(C5N2H7){[Na(H2O)2]3Co(H2O)5-[Co(H2O)]3(AsW9O33)2}•27H2O的晶体结构及性质

在pH＝7.5的水溶液中, Na₂WO₄•2H₂O, NaAsO₂, CoCl₂•6H₂O与对氨基吡啶反应, 得到了一种新的夹心型杂多钨酸盐Na₆(C₅H₇N₂){[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}•27H₂O单晶, 用X射线单晶衍射法及元素分析确定了其结构, 晶体属三斜晶系, P 空间群, 其晶胞参数为: a＝1.3276(8) nm, b＝1.7581(10) nm, c＝2.4381(14) nm, α＝70.954(9)°, β＝86.663(9)°, γ＝72.885(9)°, V＝5.136(5) nm³, Z＝2, R₁＝0.0608, wR₂＝0.0848 [I＞2σ(I)]. 在{[Na(H₂O)₂]₃Co(H₂O)₅[Co(H₂O)]₃(AsW₉O₃₃)₂}^7－阴离子中, 一个Co^2＋与聚阴离子{[Na(H₂O)₂]₃[Co(H₂O)]₃(AsW₉O₃₃)₂}^9－的一个端基氧共价连接, Co^2＋呈现出5和6两种配位数, 质子化的氨基吡啶正离子作为抗衡离子存在于晶体之中. 对标题化合物进行了IR, UV-Vis, TG-DSC表征. 对该化合物、Na₂WO₄•2H₂O及CoCl₂•6H₂O催化H₂O₂氧化乙醛的活性进行了比较研究, 该化合物的催化活性远优于简单化合物Na₂WO₄•2H₂O和CoCl₂•6H₂O.     

Guajamers A-I,Rearranged Polycyclic Phloroglucinol Meroterpenoids from Psidium guajava Leaves and Their Antibacterial Activity

Main observation and conclusion Eight new polycyclic phloroglucinol meroterpenoids guajamers A-H (1-8),a methylated benzoylphloroglucinol meroterpenoid guajamer...     

磁场对La2－xSrxCuO4单晶热导的影响研究

报道了系列欠掺杂La_2-xSr_xCuO₄（x=0063,0070,0 090,0110,0125）单晶的零场和加磁场情况下ab面和c方向的热导率与温度的关系曲线，测量 温度范围从2到45K. 研究发现ab面和c方向的热导率都受到磁场的压制. 而且在磁场 的作用下，热导压制率随温度变化的关系和场致反铁磁有序的增强与温度的依赖关系有高度 相似性. 认为磁场引起的ab面的热导压制主要是电子热导的变化所致，而c方向的 压制则可能主要来源于声子热导的变化，它们均可能与磁场诱导下欠掺杂La_2-x Sr_xCuO₄的某种电荷有序和磁有序的增强密切相关. 关键词： 热导 电荷有序 磁有序     

混合溶剂前体法制备纳米CuO粉体及其性能表征

Nano-CuO was prepared by heating nano-Cu₂(OH)₂CO₃ precursors in different calcination temperatures. The precursor was synthesized from water-alcohol mixed solution of Cu(Ac)₂ using mixed solution of NaOH and Na₂CO₃as precipitants. XRD, FT-IR, TEM, TG-DTA and surface area measurement techniques were used to investigate the properties of the CuO powder. The results show that the spherical, well dispersed nano-CuO powder with the average size of 15 nm and higher catalytic activity for H₂O₂ decomposition was obtained at 300 ℃. With the increasing of calcination temperature, crystal of CuO grows up, agglomeration of the powder becomes heavier and catalytic activity decreases. FT-IR patterns revealed that the vibration fine structure of Cu-O bond in nano-CuO powder disappears and main absorption is red-shifted with the average size of nano-CuO reducing.     

A carrier-free and recyclable protocol for the cross-coupling of terminal alkynes with arylboronic acids in H2O/TBAB

A new and recyclable protocol was developed for Pd(OAc)₂-catalyzed the cross-coupling reaction of terminal alkynes with arylboronic acids using environmentally friendly H₂O/TBAB as reaction medium. A series of cross-coupling products containing internal acetylenic bond can be obtained with good selectivity and yield. The Pd(OAc)₂/H₂O/TBAB system was stable in the Sonogashira-type cross-coupling reaction and could be used at least three cycles without considerable decrease in catalytic performance. The results suggest that the unsupported and recyclable systems can be extended to the other realm of CC bond formation in synthetic organic chemistry.     

Highly enantioselective addition of in situ prepared arylzinc to aldehydes catalyzed by a series of atropisomeric binaphthyl-derived amino alcohols

The direct addition of in situ prepared arylzinc to aldehydes with chiral binaphthyl-derived amino alcohols as catalysts can afford optically active diarylmethanols in high yields and with excellent enantioselectivities (up to 99 % ee, ee = enantiomeric excess). By using a single catalyst, both enantiomers of many pharmaceutically interesting diarylmethanols can be obtained by the proper combination of various arylzinc reagents with different aldehydes; this catalytic system also works well for the phenylation of aliphatic aldehydes to give up to 96 % ee.     

基于2,3-二羟基丁二酸新配位方式构建的新颖双U形四核铜配合物[Cu4(dhbd)2(dpphen)4•2H2O]•8H2O

利用水热法合成了标题配合物Cu₄(dhbd)₂(dpphen)₄•2H₂O]•8H₂O(H4dhbd＝2,3-二羟基丁二酸, dpphen＝4,7-二苯基-1,10-邻菲咯啉), 通过元素分析、红外光谱、热分析、X射线单晶衍射等技术对其进行了表征. 晶体结构分析表明, 由于水的配位阻断, 2,3-二羟基丁二酸根仅通过单羟基氧桥联两个U形双核亚单元形成具有一个对称中心的双U形四核结构, 其中U型亚单元包含晶体学上不对称的2个Cu(II)原子、1个2,3-二羟基丁二酸根(dhbd)、2个4,7-二苯基-1,10-邻菲咯啉(dpphen)和1个配位H₂O分子. 毗邻的四核单元通过配位H2O分子和配位羟基O原子形成的R₂²(8)型环形氢键桥的连接, 沿a轴方向构建了四核单元交替相连的一维超分子链; 链间籍苯环的π-π堆积作用和晶格水分子氢键链的连接进一步扩展为具有隧道的三维结构. 配合物中呈现了一种2,3-二羟基丁二酸与过渡金属配位的新方式. 变温磁化率研究表明标题配合物具有弱的反铁磁耦合作用.