A 3D Ba(Ⅱ) Inorganic-organic Hybrid Framework Based on 1,3,5-Benzenetricarboxylic Acid Ligand: Synthesis and Characterization

A three-dimensional（3D） barium complex with 1,3,5-benzenetricarboxylic acid（H3BTC）, {[Ba1.5（BTC）（H2O）]·（H2O）}n（1）, was synthesized in DMF/EtOH/H2O mixed solution under solvothermal conditions, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses, and photoluminescence measurement. In complex 1, the 2D I2O0 type inorganic layer is constructed by {Ba1O10} and {Ba2O9} polyhedra. Moreover, the solid-state fluorescence measurement reveals a fluorescence emission band at 465 nm under 344 nm excitation, assigned to a charge-transfer transition.

Syntheses and Magnetism of μ-1, 3, 5-Benzenetricarboxylato Trinuclear Manganese(Ⅱ) and Nickel(Ⅱ)Complexes

Two new manganese(Ⅱ ) trinuclear complexes and two new nickel (Ⅱ) trinuclear compIexes, namely, [Mn3 (BZT ) (Phen )6] (ClO4 )3 (complex 1 ), [Mn (BZT)· (Nphen )6] (ClO4 )3 (complex 2), [Ni3 (BZT) (Phen)6] (ClO4 )3· 5H2O (complex3) and [Ni3 (BZT ) (Nphen )6] (ClO4 )3 (complex 4 ) (BZT = 1, 3, 5-benzenetricarboxylato, Phen = 1, 10-phenthroline, Nphen = 5-nitro-1, 10-phenanthroline )have been synthesized. The complexes were characterized using elemental analysis,IR and electronic reflection spectra. These complexes are proposed to have extended 1, 3, 5-benzenetricarboxylato-bridged structure and to consist of three manganese (Ⅱ) or three nickel(Ⅱ). The X-band ESR spectra of the complex 1 and complex 2were recorded at room temperature. The variable-temperature magnetic susceptibilities of complex 1 and complex 3 were measured over 4. 2-300 K. According to experimental results of the variable-temperature magnetic susceptibility, the magnetic interaction between the paramagnetic centers is too weak to be detected using the usual magnetic susceptibility technique.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Syntheses,Crystal Structures and Properties of Co(Ⅱ) and Cu(Ⅱ) Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co（O2N-Hbtb）（phen）（H2O）3]·2H2O}n 1 and {[Cu3（O2N-btb）2（bipy）2（H2O）4]·4H2O}n 2（O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2＇-bipyridine）,were prepared through hydrothermal reactions of Co（Ⅱ） or Cu（Ⅱ） salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.

A New Zn(Ⅱ)Coordination Polymer Constructed from 1,3,5-Benzenetricarboxylate Ligand Exhibiting Photoluminescence

The title Zn（Ⅱ） coordination polymer {[Zn2（BTC）（HBTC）（dpa）（Hdpa）]·3H2O}n（1,H3BTC = 1,3,5-benzenetricarboxylic acid,dpa = 4,4＇-dipyridylamine）,has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder X-ray diffraction,IR spectroscopy and Fluorescence spectroscopy.Complex 1 belongs to the triclinic system,space group P1,a = 9.9415（4）,b = 13.5859（8）,c = 15.2987（5） A,α = 96.301（4）,β = 107.944（3）,γ = 103.575（4）°,V = 1873.48（14）A3,Z = 2,μ = 1.365 mm^-1,Dc = 1.672 g/cm^3,Mr = 943.44,F（000） = 964,the final R = 0.0314 and wR = 0.0710 with I 〉 2σ（I）.Complex 1 displays a two-dimensional bilayer coordination polymer.Complex 1 shows fluorescence in the solid state at room temperature.

刚性配体1,3,5-三(1-咪唑基)苯与1,2,4-苯三甲酸构筑的金属配合物：水热合成及晶体结构(英文)

由水热法合成了2个配合物[Co(1,2,4-HBTC)(tib)](1)和[Ni4(1,2,4-BTC)2(tib)4(H2O)2]·(1,2,4-HBTC).9H2O(2)(1,2,4-H3BTC=1,2,4-苯三甲酸,tib=1,3,5-三(1-咪唑基)苯),并用元素分析、红外光谱、X-射线单晶衍射及热重分析等对其进行了表征。晶体结构分析结果表明:配合物1是由Co(Ⅱ)和tib连接形成的二维层状结构,1,2,4-HBTC2-作为端基配体与Co(Ⅱ)配位,而配合物2是通过1,2,4-BTC3-连接[Ni(tib)]2+二维网形成最终的二维多层结构,这2个化合物最终均被氢键连接形成三维超分子结构。

Syntheses, Crystal Structures, and Properties of Two Mixed-ligand Coordination Polymers: [Zn(bdc)(1,3-bimb)]_n and {[Mn_2(ox)_2(1,3,5-tib)_(4/3)]·4H_2O}_n

Two new coordination polymers,[Zn（bdc）（1,3-bimb）]n（1） and {[Mn2（ox）2（1,3,5tib）4/3]·4H2O}n（2）（H2ox = oxalic acid,H2bdc = terephthalic acid,1,3-bimb = 1,3-bis（imidazol-1ylmethyl）benzene,1,3,5-tib = 1,3,5-tri（imidazol-1-yl）benzene）,were synthesized and characterized by elemental analysis,IR,powder X-ray diffraction（PXRD）,and thermogravimetric（TG） analyses.X-ray diffracation analysis reveals that two kinds of zigzag chains [Zn（bdc）]n and [Zn（1,3-bimb）]n in compound 1 are interweaved to form a 3D 4-fold interpenetrated 66-dia framework.In compound 2,Mn（1） and Mn（2） are linked via 1,3,5-tib ligands to form two different nets of [Mn6（1,3,5-tib）6 ]n along the ab plane with inner-or outer-shape N–Mn–N angles,which are connected by 1D infinite [Mn2（ox）2 ]n chains via Mn–O bonds to result in a（3,3,3,4,4）-connected（4·8·10）3（4·82）3（4·83·102）6（82·104·3）3（83）4 topology.Moreover,the photoluminescence of 1 has been investigated.The crystal of 1 crystallizes in orthorhombic,space group Pna2 with a = 13.2267（6）,b = 9.1717（4）,c = 17.4492（8）,V = 2116.79（16）3,Z = 4,C22 H18N4O4 Zn,Mr = 467.77,Dc = 1.468 g/cm3,F（000） = 960 and μ（MoKα） = 1.197 mm-1.The final R = 0.0280 and wR = 0.0618 for 3695 observed reflections with I 2（I） and R = 0.0389 and wR = 0.0653 for all data.The crystal of 2 crystallizes in rhombohedral,space group R-3 with a = 22.080（8）,c = 31.19（2）,V = 13167（11） 3,Z = 18,C24 H25 Mn2 N8 O13,Mr = 743.40,Dc = 1.688 g/cm3,F（000） = 6822 and μ（MoKα） = 0.945 mm-1.The final R = 0.0429 and wR = 0.1035 for 5160 observed reflections with I 2（I） and R = 0.0824 and wR = 0.1244 for all data.

成核剂1,3,5-苯三甲酸三(环己胺)作用下聚丙烯的等温结晶动力学研究

采用经典的Avrami方程研究了成核剂1,3,5-苯三甲酸三(环己胺)(BTCA-TCHA)作用下等规聚丙烯(iPP)的等温结晶动力学,采用阿仑尼乌斯公式计算了聚丙烯的结晶活化能。结果表明,BTCA-TCHA的加入可明显缩短聚丙烯的半结晶时间(t1/2),加快聚丙烯的结晶速度;BTCA-TCHA的加入对聚丙烯的球晶生长方式基本没有影响,空白聚丙烯和成核聚丙烯的球晶生长方式都是扩散控制的异相成核三维球晶生长。此外,成核剂的加入使聚丙烯的结晶活化能ΔE从空白聚丙烯的370 kJ/mol降低到312 kJ/mol,从而加快聚丙烯的总结晶速率。

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper(Ⅱ) Complex:[Cu_6(DPPZ)_4(btc)_4(H_2O)_8]·5H_2O

A new hexanuclear copper（Ⅱ） complex,[Cu 6 （DPPZ） 4 （btc） 4 （H 2 O） 8 ]·5H 2 O （1,DPPZ=dipyrido[3,2-a：2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid）,has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489（4）,b=14.234（5）,c=14.484（5）,α=82.848（4）,β=79.399（4）,γ=73.646（4）°,V=2421.2（13） 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F（000）=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I 2σ（Ⅰ）.In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.

Ⅱ型聚磷酸铵和赛克对聚丙烯的协同阻燃作用

对Ⅱ型聚磷酸铵(APP-II)和三(2-羟乙基)异氰尿酸酯(赛克)协同阻燃聚丙烯进行了研究。结果表明,APP-II和赛克以质量比为2.5∶1复合而成的阻燃剂对PP具有良好的协同阻燃作用。当该阻燃剂添加量为30%(质量分数)时,PP的极性氧指数(LOI)为30.7%,阻燃级别达FV-0级,燃烧时的热释放速率、质量损失速率和总热释放量明显降低。热重和燃烧残余物分析结果表明,高温下APP能够促使三(2-羟乙基)异氰尿酸酯(THEIC)和PP成炭,而APP和THEIC分解释放出的氨气使炭层膨胀,由此形成的致密膨胀炭层通过隔绝作用而产生阻燃和抑烟作用。

羧酸-含氮杂环稀土配合物的合成及荧光性能研究

以3-氨基吡嗪-2-羧酸(ampca)为阴离子配体、以2,4,6-三吡啶基三嗪(TPTZ)和1,10-邻菲罗啉(phen)为中性配体分别合成了两对钐和镝配合物;以对苯二甲酸(PTA)和TPTZ为配体合成了铽配合物.对5种配合物进行了元素分析、红外光谱、紫外光谱的测定,推测配合物的组成分别为Dy(TPTZ)(ampca)3·3H_2O(1)、Sm(TPTZ)(ampca)3·3H_2O(2)、Dy(phen)(ampca)3·4H_2O(3)、Sm(phen)(ampca)3·4H_2O(4)和Tb(TPTZ)(PTA)1.5·3H_2O(5).测定了配合物的荧光强度及荧光寿命,结果表明Tb配合物发光强度和寿命明显高于Sm,Dy的配合物;中性配体TPTZ和Phen可以明显增强钐和镝配合物的发光,其中Phen的增强作用更大.

2,4,6-三吡啶基三嗪-芳香羧酸镝配合物的合成及其荧光性能

分别以2,4,6-三吡啶基三嗪(TPTZ)、对羟基苯甲酸和对苯二甲酸为配体,以Dy3+为中心合成了不同组成的5种配合物。对其进行了元素分析、紫外光谱、红外光谱、荧光激发和发射光谱的测定。推测配合物的组成分别为:(1)Dy(TPTZ)(NO3)3(C2H5OH).H2O;(2)Dy(TPTZ)2(NO3)3(C2H5OH).H2O;(3)Dy2(TPTZ)(NO3)6(C2H5OH).2H2O;(4)Dy(TPTZ)(C7H5O3)3(C2H5OH).2H2O;(5)Dy2(TPTZ)2-(C8H4O4)(NO3)4(C2H5OH).H2O。硝酸根的氧原子、芳香酸的羧基氧和稀土离子配位,TPTZ以主配位点和中配位点的氮原子与稀土离子成键。配合物的形成对配体的共轭π-π*跃迁影响不大。荧光强度测试表明,硝酸根、不同的芳香羧酸作为阴离子配体的镝配合物的发光强度有很大差别。芳香羧酸配体对镝配合物的荧光增强最大,镝离子浓度高,荧光强度也高。配合物(2)荧光强度大于配合物(1),配合物(3)荧光强度大于配合物(2),可见配体TPTZ多或者发光离子浓度高则配合物发光强度高;配合物(4)荧光强度强于配合物(1),表明对羟基苯甲酸吸收和传递光能强于硝酸根;配合物(5)的荧光强度是5个配合物中最高的,表明对苯二甲酸三重态能级与Dy3+的最低激发态能级匹配,对光的吸收和传递也好,同时也看出发光的Dy3+离子量增加,配合物的发光强度增强。

Three Isomeric Chiral Metal-organic Frameworks Determined by Different Halogen Ions

Three isomeric metal-organic frameworks,[Cd2（X）（btc）（DMA）3]n（X = Cl（1）,Br（2）,I（3）,H3btc =1,3,5-benzenetricarboxylic acid and DMA = N,Nˊ-dimethylacetamide）,have been synthesized and characterized by elemental analysis,infrared spectra（IR）,thermogravimetric（TG） analyses and single-crystal X-ray diffraction.Single-crystal X-ray analysis reveals that compounds 1–3 crystallize in the orthorhombic P212121 space group,and feature a three-dimensional（3D） extended framework containing dinuclear [Cd2（COO）3] units as the secondary building units（SBUs）.Topological analysis reveals that compounds 1–3 can be simplified into a 3-connected srs topological network.

鹿蹄草中一个新的萘醌类化合物

为了研究鹿蹄草中止血活性提取物的化学成分,采用色谱方法对其进行了分离纯化。除一些已知成分外,分离得到了一个新的萘醌衍生物,通过理化性质和光谱数据分析,鉴定为2-(1,4-二氢-2,6-二甲基-1,4-二氧代-3-萘基)-3,4,5-三羟基苯甲酸。