Influence of the reaction temperature and ph on the coordination modes of the 1,4-benzenedicarboxylate (BDC) ligand: a case study of the Ni(II)(BDC)/2,2'-bipyridine system

Three new Ni(BDC)/2,2'-bipy compounds, Ni2(BDC)(HBDC)2(2,2'-bipy)2 (2), Ni3(BDC)3(2,2'-bipy)2 (3), and Ni(BDC)(2,2-bipy)2.2H2O (5), in addition to the previously reported Ni(BDC)(2,2'-bipy).0.75H2BDC (1) and Ni(BDC)(2,2'-bipy)(H2O) (4) [BDC = 1,4-benzenedicarboxylate; 2,2'-bipy = 2,2'-bipyridine], have been synthesized by hydrothermal reactions. A systematic investigation of the effect of the reaction temperature and pH resulted in a series of compounds with different compositions and dimensionality. The diverse product slate illustrates the marked sensitivity of the structural chemistry of polycarboxylate aromatic ligands to synthesis conditions. Compound 1, which has a channel structure containing guest H2BDC molecules, is formed at the lowest pH. The guest H2BDC molecules are connected by hydrogen bonds and form extended chains. At a slightly higher pH, a dimeric molecular compound 2 is formed with a lower number of protonated carboxylate groups per nickel atom and per BDC ligand. Reactions at higher temperature and the same pH lead to the transformation of 1 and 2 into the two-dimensional, layered trinuclear compound 3. As the pH is increased, a one-dimensional polymer 4 is formed with a water molecule coordinated to Ni2+. Bis-monodentate and bischelating BDC ligands alternate along the chain to give a crankshaft rather than a regular zigzag arrangement. A further increase of the pH leads to the one-dimensional chain compound 5, which has two chelating 2,2'-bipy ligands. Crystal data: 2, triclinic, space group P, a = 7.4896(9) angstroms, b = 9.912(1) angstroms, c = 13.508(2) angstroms, alpha = 86.390(2) degrees , beta = 75.825(2) degrees, gamma = 79.612(2) degrees, Z = 2; 3, orthorhombic, space group Pbca, a = 9.626(2) angstroms, b = 17.980(3) angstroms, c = 25.131(5) angstroms, Z = 4; 5, orthorhombic, space group Pbcn, a = 14.266(2) angstroms, b = 10.692(2) angstroms, c = 17.171(2) angstroms, Z = 8.     

High-efficiency, environment-friendly electroluminescent polymers with stable high work function metal as a cathode: green- and yellow-emitting conjugated polyfluorene polyelectrolytes and their neutral precursors

A series of aminoalkyl-substituted polyfluorene copolymers with benzothiadiazole (BTDZ) of different content were synthesized by Suzuki coupling reaction, and their quaternized ammonium polyelectrolyte derivatives were obtained through a postpolymerization treatment on the terminal amino groups. Copolymers are soluble in environmentally friendlier solvents, such as alcohols. It was found that the efficient energy transfer occurs by exciton trapping on the narrow band gap BTDZ site under UV illumination. Only 1% of BTDZ content is needed to completely quench a fluorene emission for both the neutral and the quaternized copolymers in the neat film. Absolute PL efficiencies of copolymer films were greatly enhanced as a result of the suppression of excimer formation. Light-emitting devices fabricated from these copolymers show high external quantum efficiencies over 3% and 1% for the neutral precursor and the quaternized copolymers, respectively, with high work function metals such as Al as a cathode. To the best of our knowledge, this is the first report on an electroluminescent polymer which bears the high EL efficiency, the electron-injection ability from high work function metals, and the solubility in environment-friendly solvents at the same time. These features make them a promising candidate for the next generation of light-emitting copolymers in PLED flat panel display application.     

从头计算方法比较TiSi_2的C54相和C49相

采用平面波超软赝势描述多电子体系,利用密度泛函理论和广义梯度近似,计算出C54相和C49相TiSi2的晶格常数、体弹性模量、形成能、电子态密度(DOS)和Mulliken电荷布居等性质.通过比较这两种物质的性质,发现尽管两者形成能很相近,但C49相结构对称性差、体弹性模量小、熔点低,Ti原子d轨道的反键强、离子性弱.这些性质上的差异和C49相TiSi2在固相反应中优先形成有关.     

A Large Conformational Change of a Bridged β-Cyclodextrin Dimer in Aqueous Solution

A novel bridged β-CD dimer in which two β-cyclodextrins were linked by a naphthalene at positions 2 and 7 has been synthesized. 1H and 13CNMR measurements showed that a large change in the conformation of the dimer occurred in aqueous solution. The dimer interacted with methyl and ethyl orange to form stable inclusion complexes via "induced fit" mechanism.     

一维链配位聚合物[Mn(acacen){N(CN)2}]n的合成、结构和性质的研究(英)

The manganese(Ⅲ) complex [Mn(acacen){N(CN)₂}]_n [H₂acacen=bis(acetylacetone)ethylenediimine] has been synthesized and the structure has been determined. The complex forms a one-dimensional chain structure via the bidentate bridge ligand μ_1,5-[N(CN)₂]^- linking [Mn(acacen)] moiety. The magnetic property of the compound (75～300 K) shows the existence of an antiferromagnetic exchange interaction among paramagnetic centers along the chain. CCDC: 244940.     

Keggin类杂多化合物催化α,β-不饱和羰基化合物环氧化

在乙睛溶剂中考察了一系列杂多化合物和过氧化氢水溶液催化的各种缺电子的α,β-不饱和羰基化合物的环氧化反应.在所研究的杂多化合物中,二缺位的[γ-SiW10(H2O)2O34](Bu4N)4显示出了最高的活性.     

水溶性含C_(60)聚电解质的制备及其与重氮树脂自组装膜AFMFFM的初步研究

通过BPO引发的溶液聚合 ,合成了水溶性的星状C6 0 苯乙烯 苯乙烯磺酸钠的三元共聚物 [Star shapedC6 0 poly(St SS) ],运用自组装技术 ,在水溶液中 ,含C6 0 的三元共聚物与重氮树脂 (Diazoresin)通过正负离子间的吸附力在云母基片上交替一层一层有序地组装成固体膜 .自组装膜经紫外光幅照反应 ,通过重氮基的分解 ,层间连接的离子键转变成共价键 ,从而增加薄膜的稳定性和堆砌密度 .用原子力显微镜 摩擦力显微镜(AFM FFM)考察了C6 0 在膜中的承载作用及比较不同链结构、不同链长、不同层数自组装膜的表面形貌和微摩擦性能 .初步的研究结果显示了聚合物薄膜的微摩擦性能与聚合物的化学结构、链长和膜的层数有密切关系     

用高效疏水色谱法对多种脲变α-淀粉酶折叠中间体的研究

用高效疏水色谱法对用脲变性的α-淀粉酶的体外折叠中间体进行了分离，发现脲变α-淀粉酶折叠至少有19个中间体，而且，这些中间体在色谱流出液中可稳定一周．这一结论已由电泳、离子交换色谱和体积排阻色谱法证实．此外，还用紫外吸收光谱和荧光发射光谱研究了这些折叠中间体与天然α-淀粉酶构象之间的差异．