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.     

CuZnAl水滑石衍生催化剂上甲醇水蒸气重整制氢Ⅲ.合成水滑石用金属盐的影响

采用共沉淀法,用不同金属盐为Cu源和Zn源合成了一系列CuZnAl水滑石,以此为前体经600℃焙烧后制得相应催化剂.用硝酸盐和醋酸盐合成的水滑石结晶度高,其衍生催化剂比表面积大、Cu的分散性好且易于还原;而用硫酸盐和盐酸盐合成的水滑石结晶度差,其衍生催化剂比表面积小、Cu的分散性差且不易还原.反应评价结果显示,用硝酸盐和醋酸盐制得的催化剂活性高、反应稳定性好;而用硫酸盐和盐酸盐制得的催化剂由于低的Cu表面积以及S和Cl的毒化作用而几乎无催化活性.在醋酸盐制备的催化剂上,产物干气中CO的浓度明显较低,在250℃和WHSV=3.28 h-1的条件下约为0.03%~0.04%,仅为硝酸盐所制催化剂上CO浓度的1/5;在210℃和WHSV=0.5 h-1的条件下,该催化剂上甲醇几乎完全转化,同时CO浓度降至约0.005%.N2O滴定、CO2程序升温脱附和程序升温还原结果显示,用醋酸盐和硝酸盐制备的催化剂具有极相近的Cu表面积和表面碱性,但前者CuO的还原峰温较后者低近70℃,归因于ZnO与CuO间的强相互作用,这是催化剂具有良好选择性的可能原因.     

Hydroxylation of nigranoic acid to 6β-hydroxynigranoic acid by Caryospora carllicarpa YMF1.01026

Microbial transformation of nigranoic acid by Caryospora carllicarpa YMF1.01026 afforded the new derivative 6β-hydro-xynigranoic acid. Its structure was elucidated by spectroscopic methods.