Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

The Synthesis and Absorption Character of New Bis (dithiobenzil) nickel Complex NIR Dyes

A series of new NIR dyes bearing 4-(4-morpholinyl) phenyl and substituted phenyl, were synthesized. The maximum absorption wavelengths of these dyes range from 928 nm to 990 nm.

Synthesis, Crystal Structure, and Catalytic Performance of 2,6-Bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine Nickel(Ⅱ) Complex

A novel nickel（II）-complex Ni[L]Cl2-CH3CN（1） containing the tridentate ligand 2,6-bis[1-（2,4,6- trimethylphenylimino）ethyl]pyridine（L） has been synthesized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction analysis. The catalytic activity of complex 1 for the polymerization of ethylene was studied under activation with methylaluminoxane（MAO）.

Two Nickel(Ⅱ) Complexes Constructed by Novel Bis(3-methoxy-2-pyridyl)ether-6,6′-dicarboxylic Acid Ligand:Lattice Water Control of Structure

Under given conditions, two complexes of [Ni（H20）2BEDA]·2H2O 1 and [Ni（Py）2- BEDA]·6H2O 2 （BEDA = bis（3-methoxy-2-pyridyl）ether-6,6′-dicarboxylic acid） have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Crystal data for 1： C14H18NiN2O11, monoelinic C2/c, a = 14.3844（17）, b = 12.9900（15）, c = 9.6309（11） A, β = 104.3350（10）°, V= 1743.5（4） A3, Z = 4, Dc= 1.711 g/cm^3, F（000） = 928, μ = 1.179 mm^-1, Mr= 449.01, the final R = 0.0228 and wR = 0.0625. Crystal data for 2： C24H32NiN4O13, triclinic P1, a = 9.423（2）, b = 11.863（3）, c = 13.089（3） A, α = 91.511（3）, β = 92.465（3）, γ = 100.696（2）°, V = 1435.6（6） A^3, Z = 2, Dc= 1.488 g/cm^3, F（000） = 672, μ = 0.748 mm^-1, Mr= 643.25, the final R = 0.0400 and wR = 0.0975. Interestingly, in the two complexes, lattice water molecules dominate its crystal structures. Therefore, extensive intermolecular hydrogen bonds assemble 1 and 2 into 2D extended sheets and a 3D open framework, respectively. Furthermore, water molecules present in 2 are associated to form water clusters.

Synthesis, Structure, and Luminescence of a New Nickel(Ⅱ) Coordination Polymer Based on 2,6-Bis(4'-carboxyphenyl)-4-phenylpyridine

Solvothermal reaction of aromatic 2,6-bis（4＇-carboxyphenyl）-4-phenylpyridine （H2bpp） ligand and nickel cation in the presence of 1,10-phenanthroline （phen） affords one new coordination polymer （CPs）, [Ni（bpp）（phen）（H20]n （1）. The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analyses, IR, PXRD and luminescence. Ions of Nin in 1 are linked via bpp2 to form chains, which are further connected through non-covalent interactions （including O-H...O and n...zr interactions） to form a 3D packing diagram. The crystal ofl crystallizes in triclinic, space group PI with a = 10.998（10）, b = 12.019（10）, c = 12.485（11） A, a = 75.774（14）, β = 85.828（16）, y = 66.542（13）°, V= 1467（2）/k^3, Z = 2, C38H26N2O5Ni, Mr= 649.32, Dc = 1.470 g/cm^3, F（000） = 672 andμ（MoKa） = 0.721 mm-1. The final R = 0.0692 and wR = 0.1048 for 5116 observed reflections with/〉 20（/） andR = 0.0874 and wR = 0.1364 for all data.

Hydrothermal Synthesis, Crystal Structure and Surface Photo-electric Properties of a New Nickel(Ⅱ) 3-D Metalorganic Framework Constructed from the Rigid 1,4-Bis(imidazol-1-yl) benzene Ligand

A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy（SPS）. Complex 1 crystallizes in monoclinic system, space group C2/c with a = 19.5988（6）, b = 9.7531（3）, c = 11.8146（4） ？, β = 96.185（3）°, V = 2245.20（12） ？~3, C_（24）H_（20）N_8NiO_4S, M_r = 575.25, D_c = 1.702 g/cm^3, Z = 4, F（000） = 1184, μ = 1.011 mm-1, the final R = 0.0293 and w R = 0.0702. X-ray diffraction analyses indicated that the center Ni^（2＋） ion is six-coordinated with an O_2N_4 donor set of two μ_2-SO_4^（2–） and four bib ligands, resulting in an ideal octahedral geometry. Topological analysis on complex 1 considers each Ni^（2＋） as a 6-connected node, while bib and sulfate ion as linkers, giving an α-Po topology with short Schl？fli symbol 412·63. In the crystal packing, the components interact with pairs of intermolecular C–H×××O hydrogen bonds. The SPS of 1 indicates that there are positive response bands in the range of 300~600 nm showing photo-electric conversion properties.

Hydrothermal Synthesis and Crystal Structure of One 3D Coordination Polymer of Nickel(Ⅱ) Achieved from 5-Iodo-isophthalic Acid Ligand

A new coordination polymer [Ni（L）（m-bix）（H2O）]n （1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis（imidazol-1-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638（3）, b = 10.2319（3）, c = 13.2463（4） ？, α = 80.1710（10）, β = 83.671（2）, γ = 70.3790（10）o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85（6） ？3, Dc = 1.746 g/cm3, F（000） = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ（I）. In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric （TG） and differential thermal analysis （DTA）.

Synthesis and Crystal Structure of [Ni(bdpm)_2(OAc)]_2(N_3)_2·5H_2O(bdpm=Bis(3,5-dimethylpyrazol-1-yl)methane,OAc=CH_3COO^-)

A Ni（Ⅱ） complex [Ni（bdpm）2（OAc）]2（N3）2.5H20 （bdpm = bis（3,5-dimethylpyrazol-1-yl）-methane） was synthesized and characterized by elemental analysis, 1R and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 18.630（2）, b = 16.6624（19）, c = 19.821（2） A, fl = 90.146（2）°, V = 6152.9（12） A3, Z = 4, C48H80N22Ni2O9, Mr = 1226.76, Dc = 1.324 g/cm^3, F（000） = 2600 and μ = 0.680 mm^-1. The structure was refined to the final R = 0.0578 and wR = 0.1337 for 10848 independent reflections （Rint = 0.0311） and 6915 observed reflections （1 〉 2σ（I））. The complex contains two asymmetric molecules in the cell with small difference in bond distances and bond angles. Each Ni（Ⅱ） ion is bound by four nitrogen atoms of two chelating bdpm groups in a six-membered boat conformation and two oxygen atoms from one chelating bidentate acetate group to form a distorted octahedral geometry. The complex also contains azide anion outside acting as counteranion and two crystalline water molecules to link two discrete mononuclear cations though hydrogen bonds.

Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand： Assembly, Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.

A Novel Humidity-Sensitive Material Based on PDEB with Nickel Complex Catalyst

Poly(p-diethynylbenzene) (PDEB) with improved solubility was synthesized using a novel catalyst bis(triphenylphosphine)bis(p-diethynylbenzene) nickel complex (NI-C). A surface acoustic wave (SAW) delay line oscillator was covered by Langmuir-Blodgett (LB) films of resulting PDEB to prepare a humidity sensor, which was found to have high sensitivity and good repeatability. PDEB shows promise as a good humidity-sensitive material.

泡沫镍原位生长普鲁士蓝类似物构筑镍铁双金属氧化物催化剂的氧析出反应性能研究

开发高性能、低成本的氧析出反应(OER)催化剂对促进电解水制氢降低电耗、提高经济性具有重要意义。以导电泡沫镍为基底,采用冰水浴法原位生长镍铁普鲁士蓝类似物,氧化制备了镍铁双金属氧化物催化剂。分别采用X射线衍射、扫描电镜、高分辨率透射电镜和X射线光电子能谱方法对催化剂的物相组成、微观形貌和表面化学状态进行了表征,并采用电化学测试表征了催化剂的OER催化性能。结果表明,当氧化温度为200℃、氧化时间为2 h时,制备的催化剂中镍铁双金属氧化物高度分散在泡沫镍基底上,纳米颗粒最小,平均粒径为71 nm,可暴露的催化反应活性位点多,表现出最优的OER催化性能。该催化剂在1.0 mol/L的KOH电解液中,电流密度为10 mA/cm^(2)时,过电位仅为272 mV,并在电流密度为100 mA/cm^(2)时稳定运行了40 h,表现出优异的OER电化学稳定性。

二氰基二硫纶和邻菲罗啉二酮的镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物的合成与性质

二氰基二硫纶和邻菲罗啉二酮的镍（Ⅱ）、铜（Ⅱ）、锌（Ⅱ）配合物的合成与性质彭正合＊潘庆才ａ任小明ｂ张克立秦子斌（武汉大学化学系，武汉４３００７２；ａ南京大学配位化学国家重点实验室，南京２１００９３）关键词：二硫纶邻菲罗啉二酮镍铜锌二硫纶（ｄｉｔｈｉｏ...

硫代双烯镍近红外染料的合成及性质

该文分别通过安息香路线和二酮路线合成了4种具有不同取代基的硫代双烯镍近红外染料,并考察了染料的物理、光电化学及热稳定性等性质。紫外-可见-近红外(UV-Vis-NIR)吸收光谱测试结果表明,配合物在700～1 100 nm都具有较强的吸收。对化合物的取代基效应及溶剂效应的研究发现:供电子基团导致λmax红移,而吸电子基团导致λmax蓝移,且λmax随着溶剂极性增大而增大。利用循环伏安法和差分脉冲伏安法(CV/DPV)测试了化合物的电化学性质。此外,该文还通过密度泛函理论(DFT)对化合物的HOMO和LUMO能级进行了计算。热失重测试研究表明,合成的化合物具有较好的热稳定性。

二氰基二硫纶·联吡啶锦（Ⅱ）、铜（Ⅱ）、锌（Ⅱ）配合物的合成与表征

以ｃｉｓ－１，２－二氰基乙烯－１，２－二硫醇钠Ｎａ２（ｍｎｔ）和２，２＇－联吡啶金属配合物Ｍ（ｂｕｙ）Ｃｌ２为原料，合成了标题配合物Ｍ（ｍｎｔ）（ｂｐｙ），Ｍ＝Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ），并经元素分析、热谱、摩尔电导、红外和电子光谱所表征．三者均为四配位的电中性配合物，热分解温度高于３１０℃，可溶于ＤＭＦ、ＤＭＳＯ、吡啶、氯仿和丙酮，难溶于水和乙醚．

四-(3,4-二甲氧基苯基)硫代双烯合镍的合成与光谱性能

以中间体二-(3,4-二甲氧基苯基)乙二酮为原料,经过P2S5硫化、镍络合,合成了四-(3,4-二甲氧基苯基)硫代双烯镍络合物近红外吸收染料.利用IR和1HNMR表征了最终产物硫代双烯合镍的结构.考察了四-(3,4-二甲氧基苯基)硫代双烯合镍在不同溶剂中的最大吸收波长及其光、热稳定性.

萃取分离-石墨炉原子吸收光谱法测定铁镍基高温合金中砷、铅、锡、锑、铋

基于砷、铅、锡、锑、铋与碘离子形成络合物，用MIBK萃取使其与基体分离，用石墨炉原子吸收光谱法测定了铁镍基高温合金中这五种元素。文章主要对萃取条件及萃取后剩余基体对待测元素的影响进行了研究，同时采用掩蔽的方法消除了合金中钨、铌、钽的干扰。在所选定的实验条件下，测得砷、铅、锡、锑、铋的回收率范围为93％～99％；相对标准偏差范围为8．8％～12％。

新显色剂2,2-二(3,3′-二磺酸基)重氮氨基偶氮苯基丙烷的合成及其应用

合成了 2 ,2 -二 ( 3,3′-二磺酸基 )重氮氨基偶氮苯基丙烷 ( BDSDAAP) ,并研究了其与镍的显色反应条件。结果表明 ,在 p H1 0 .97的 Na2 B4 O7- Na OH缓冲溶液中 ,表面活性剂 Tween- 80存在下 ,镍与 BDSDAAP可形成一种稳定的 1∶ 2红色配合物 ,其最大吸收波长位于 5 4 0 nm,表观摩尔吸光系数 ε54 0 =2 .0 6× 1 0 5L· mol- 1·cm- 1,Ni( )在 0～ 1 5 μg/2 5 m L范围内符合比耳定律。结合萃取分离 ,应用于人发、大米和油菜中镍的测定 。

石墨炉原子吸收法测定高纯镍中痕量铋

本文利用石墨炉原子吸收法 ,在等温平台条件下直接测定了高纯镍中的痕量铋。并对石墨炉加热程序中的干燥时间、灰化温度及原子化温度进行了优化 ,同时也考察了介质酸度的影响。试验表明 :基体镍对铋的测定有显著的影响 ,为此对标准系列进行了基体匹配。本方法的特征质量为 6.1pg,相对标准偏差为 3.6% ,加标回收率为 99.3%— 10 4 %

基于2,6-二(2-苯并咪唑基)吡啶配体的锌(Ⅱ)、镍(Ⅱ)配合物的合成、晶体结构及荧光性质

通过水热反应,合成了2,6-二(2-苯并咪唑基)吡啶(BBPY)和2,6-吡啶二羧酸(DPA)的锌髤配合物[Zn(BBPY)(DPA)].H2O(1)及镍髤配合物[Ni(BBPY)2]SO4(2)。对它们进行了元素分析、红外光谱、热重等表征,并用X-射线单晶衍射测定了配合物的晶体结构。配合物1属单斜晶系,Cc空间群,晶胞参数a=1.6945(12)nm,b=1.2721(9)nm,c=1.0658(7)nm,β=92.506(12)°。配体2,6-二(2-苯并咪唑基)吡啶中的3个氮原子与2,6-吡啶二羧酸中的1个氮和2个羧基氧原子与锌髤配位,形成六配位的畸变八面体构型;配合物2也属单斜晶系,P21/c空间群,晶胞参数a=1.3735(8)nm,b=1.3838(8)nm,c=2.0270(11)nm,β=106.133(10)°。配体中每个2,6-二(2-苯并咪唑基)吡啶中的3个氮原子与镍髤配位,也形成六配位的畸变八面体构型。室温固态荧光测试显示,配合物1在428.9 nm(λmax)处具有强的荧光发射。