Hydrothermal Synthesis,Crystal Structure and Proton Conductivity of a Pr–Ca Heterometal-organic Framework Generated by 1,2,4,5-Benzenetetracarboxylic Acid

A heterometal-organic framework {[Pr2Ca（betc）2（H2O）7]·H2O}n（1） was prepared by the hydrothermal reaction of 1,2,4,5-benzenetetracarboxylic acid（H4betc） with Pr（NO3）3 and CaCO3, and further characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Complex 1 crystallizes in triclinic, space group P1 with a = 7.3668（12）, b = 10.1726（14）, c = 11.2264（15） A, a = 100.404（2）, b = 106.113（3）, g = 109.158（3）o, V = 728.48（19） A3, Mr = 966.26, Z = 1, F（000） = 470, Dc = 2.203 g/cm3, m（Mo Kα） = 3.585 mm-1, the final R = 0.0195 and w R = 0.0470（I 〉 2s（I））. Complex 1 is a 3D network with pcu topology with 1D porosity and rich hydrogen-bonding interactions. The proton conductivity of complex 1 was also studied under ~97% relative humidity and the different temperature conditions.

Synthesis and Characterization of a Proton-transfer Complex of 1,2,4,5-benzenetetracarboxylic Acid with 1,10-phenanthroline

A proton-transfer complex of 1,2,4,5-benzenetetracarboxylic acid（H4 BTC）with 1,10-phenanthroline（phen）[（H2BTC）^2-·2（Hphen）^＋·（H4BTC）]was synthesized and characterized by IR,UV-Vis spectra and luminescence. The structure was determined by X-ray single crystal diffraction.It crystallizes in the triclinic system,space group P-1 with a=7.3767（15）,b=10.704（2）,c=12.890（3）A.α=102.96（3）,β105.71（3）,γ=99.68（3）°,V=926.0（3）A^3,Dc=1.558g/cm^3,Z=2,μ（Mo-Kα）=0.121mm^-1 and F（000）=448.The final R=0.0401 and wR=0.0862 for 2983 observe reflections with[1〉2σ（I）].It is composed of discrete H4 BTC molecules,H2BTC^2- ANIONS AND [Hphen]^＋ cations.The extensive hydrogen-bonding associations fonned between the H4 BTC molecules and H2BTC^2- anions result in the formation of a two-dimensional layer,to which the [Hphen]^＋ cations are attached through the hydrogen bonds formed between the carboxyl groups of H4 BTC and the NH groups of [Hphen]^＋.Under the excitation of UV light.it emits an intense blue luminescence.

Structural Characterization and Proton-conductive Property of a Lanthanide Metal-organic Framework Assembled from 1,2,4,5-Benzenetetracarboxylic Acid and Piperazine

The reaction of Pr（Ⅲ） salt with 1,2,4,5-benzenetetracarboxylic acid（H4betc） and piperazine（pip） yielded a lanthanide metal-organic framework {[Pr（betc）（H2O）2]（H2pip）0.5}n（1）under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray structural analysis, elemental analysis, IR, X-ray powder diffraction, and thermal gravimetric. Compound 1crystallizes in monoclinic, space group P21/n with a = 11.023（5）, b = 11.109（5）, c = 11.456（5） A, β = 110.065（5）°, V = 1317.7（9） A3, Mr = 471.14, Z = 4, F（000） = 920, Dc = 2.375 g/cm^3, μ（Mo Kα） = 3.761 mm-1, the final R = 0.0286 and w R = 0.0821（I 〉 2σ（I））. Compound 1 exhibits a 2D network with（4, 4） topology, and a 3D supramolecular framework formed by hydrogen-bonding interactions. The proton conductivity of compound 1 has been investigated at ~97% relative humidity and different temperature.

Solvothermal Synthesis, Crystal Structure and Luminescent Property of a Dy(Ⅲ) Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylic Acid

A three-dimensional coordination polymer {[Dy（H2btec）2/4（btec）3/6（H2O）]·2H2O} n has been synthesized through the reaction of DyCl3·6H2O and 1,2,4,5-benzenetetracarboxylic acid by solvothermal technique, and the crystal structure was determined by X-ray diffraction. The Dy（Ⅲ） coordination polymer crystallizes in monoclinic, space group P21/n with a=10.7063（1）, b=7.1491（1）, c=17.1197（3）, α=90, β=97.10, γ=90°, V=1300.31（3）3 , C10H9DyO11 , Dc=2.389g/cm3 , Z=4, F（000）=892, the final R=0.0165 and wR=0.0448 for I 〉 2σ（I）. The title coordination polymer possesses a three-dimensional framework consisting of nine-coordinate Dy（Ⅲ） centers and two kinds of coordination modes for the 1,2,4,5-benzenetetracarboxylic acid ligands. Every btec4- ligand （deprotonated four protons from 1,2,4,5-benzenetetracarboxylic acid） in the title coordination polymer can clamp three Dy atoms like forceps, which could make the Dy atoms closer in the area of metal-metal interaction. The 3-D framework of the coordination polymer has many channels occupied by the free guest water molecules, and the hydrogen bonds between the coordinated carboxylic groups and guest water molecules could stabilize the crystal structure of the title coordination polymer. In addition, the luminescence properties were also studied.

Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(Ⅲ) with benzene-1,2,4,5-tetracarboxylic acid and 4,4′-bipyridine

A new lanthanum complex formulated as {（bpyH2）[La（btc）（H2O）4（NO3）]·2H2O}n （1） （btcH4=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4＇-bipyridine） was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806（7） nm, b=1.10258（5） nm, c=1.60333（8） nm and β=101.9400（10）°. The complex was polymeric with La^III atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The LaIn atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding （of the types of O-H…O, N-H…O and C-H…O） and ion pairing interactions connected the various components into a supramolecular structure.

环氧树脂潜伏性固化剂1,2,4,5-苯四甲酸/2-甲基咪唑盐的制备及表征

采用1,2,4,5-苯四甲酸(PMA)对2-甲基咪唑(2MZ)进行改性,制备了咪唑盐类环氧树脂潜伏性固化剂,并对其结构进行了红外光谱(FTIR)分析。考察了环氧树脂(E51)与2MZ、PMA/2MZ盐固化体系的贮存稳定性及凝胶时间。采用差示扫描量热法(DSC)研究了E51-2MZ及E51-PMA/2MZ体系的非等温固化行为,通过Kissinger模型和Ozawa模型得到了两种体系的固化反应表观活化能(Ea)、Arrheniums指前因子(A)、反应级数(n)、反应速率常数(k)等动力学参数。采用动态热机械分析(DMA)测试了E51-2MZ及E51-PMA/2MZ固化产物的玻璃化转变温度(Tg)。

1,2,4,5-苯四甲酸与稀土镨(Ⅲ)的溶剂热合成、晶体结构与性能分析

以溶剂热法合成了一种结构新颖的稀土金属配合物[Pr_2(H_2btc)(btc)(H_2O)_2]_n,[1,2,4,5-均苯四甲酸(btcH_4);均苯四甲酸二氢根(H_2btc);均苯四甲酸根(btc)]。并对该化合物进行了红外、元素分析,X射线粉末衍射分析、热重分析和晶体结构分析。从结构分析中,发现目标化合物中Pr(Ⅲ)稀土金属离子与羧基氧原子和水中氧原子配位成键而生成九配位的配聚物,其中化合物通过[btcH_2]^(2-)和btc^(4-)交替连接而形成三维木梯型的空间拓扑结构。

Hydrothermal Synthesis and Structure of a New 3D Lanthanide-Carboxylate Framework,[La(btec)_(1/2)(H_2btec)_(1/2)(H_2O)]_n(H_4 btec=1,2,4,5-Benzenetetracarboxylic acid)

The title complex, \[La(btec) 1/2 (H 2 btec) 1/2 [KG*6](H 2 O)\] n n (H 4 btec=1,2,4,5 benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5 benzenetetracarboxylic dianhydride with La(NO 3 ) 3 ·6H 2 O in H 2 O, and crystallizes in the triclinic system, space group P 1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, α = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)° , V = 1.60968(10) nm 3 , Z =2, and final R = 0.0274 , R w = 0.0735. In 1, each La(III) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H 4 btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.

铕(Ⅲ)与1,2,4,5—苯四甲酸及1,10—邻菲咯啉混配配合物的合成和荧光性质研究

在乙醇和水的混合溶剂中 ,合成了 Eu( )与 1,2 ,4,5—苯四甲酸 (H4TCB)及 1,10—邻菲咯啉混配配合物。通过元素分析、热谱分析和摩尔电导确定其化学组成为 Eu4/3 (TCB) (phen)· 4H2 O,并利用红外光谱、紫外光谱和 X射线粉末衍射对配合物进行了表征。

3,6-二肼基-1,2,4,5-四嗪二硝基水杨酸盐的合成、热分解及生成焓研究

以3,6-二肼基四嗪(DHT)和3,5-二硝基水杨酸(DNS)为原料,合成了3,6-二肼基-1,2,4,5-四嗪二硝基水杨酸盐二水合物(DHT·2DNS·2H2O),采用核磁共振波谱、红外光谱、元素分析及热重法对其结构进行了表征。采用差示扫描量热法(DSC)并结合热重-红外联用(TG-FTIR)对无水DHT·2DNS的热行为及热分解产物进行了研究。利用氧弹量热仪测定了DHT·2DNS的恒容燃烧热(ΔcU),并通过ΔcU估算了标准摩尔燃烧焓(ΔcHm)和标准摩尔生成焓(ΔfHm)。结果表明,DHT·2DNS的热稳定性要高于DHT,其受热分解可分为4个阶段:首先DHT·2DNS的二硝基水杨酸离子脱去羟基和部分硝基、羧基,同时肼基发生分解;然后苯环上的基团与四嗪环发生解离;随后苯环发生裂解;最后苯环残余物继续发生分解。DHT·2DNS的ΔcU值、ΔcHm值和ΔfHm值分别为(-11 938.17±25.33)J/g、(-7 119.77±15.16)kJ/mol和(-1 177.2±11.14)kJ/mol。

1,2,4,5—苯四酚—四乙酸光度比浊法测定水样中钾含量的研究

研究了在聚乙烯醇介质中 ,钾离子与 1 ,2 ,4 ,5—苯四酚—四乙酸形成稳定的胶体沉淀 ,钾含量在 0～ 4 8mg/ L内符合比耳定律 ,方法可用于水样中钾含量的测定 。

Synthesis and crystal structure of polymer cobalt(II) complex, 1,2,4,5-benzenetetracarboxylate hexaimidazole tetraaqua cobalt (II) tetrahydrate

The crystal structure of the title complex { [ Co (TCB)2/2-(IMI)2(H2O)2][Co(IMI)4(H2O)2]}[(H2O)4 (where TCB = 1,2,4,5-benzenetetracarboxylic anion; IMI= imidazole) has been determined by X-ray diffraction method. Crystal data for {[Co(TCB)2/2(IMI)2(H2O)2][Co(IMI)4(H2O)2]}-(H2O)4: triclinic, space group P 1, a = 1.0647(2) nm, b =1.1165(1) nm, c = 1.00361(1) nm, α = 91.56(1)°, β = 111.34(1)°, γ= 115.642(10)°, V = 0.9772(3) nm3, Z = l. The polymer cobalt(II) complex has a novel three-dimension network structure. Co(1) atom and Co(2) atom both are coordinated in an octahedral arrangement and located in the center of the coordination anion and the center of the coordination cation, respectively. Moreover four carboxyl groups of TCB are divided into two types, two para-carboxyl groups bridge Co (1) atom in monodentate fashion and other two para-carboxyl groups are in free.

Synthesis and Crystal Structure of a New Double 2D Layer Complex Assembled by H_4btec

Assembly of H4btec with cobalt（Ⅱ） acetate afforded a new double 2D layer coordination polymer, [Co（bteC）1/2（H2O）4·2H2O]n （H4btec = benzene-1,2,4,5-tetracarboxylic acid） 1. The polymeric structure has been characterized by single-crystal X-ray diffraction, FT-IR and thermal analysis. The crystal is of triclinic, space group PI with a = 10.8762（2）, b = 11.1411（1）, c = 11.5084（3） A, a = 82.8950（10）, β = 63.0050（10）, γ = 62.1500（10）°, V = 1091.72（4） A^3, C5H13CoO10, Mr= 292.08, Z = 4, Dc = 1.777 g/cm^3, μ = 1.612 mm^-l, F（000） = 600, R = 0.0578, and wR = 0.2162 for 3576 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Complex 1 consists of a new double 2D layer structure [Co（btec）1/2（H2O）4]n, both consisting of 4 ＋ 4 grids with the sizes of 11.3667（2）A × 11.5084（3）A （Co（1）-Co（1A） × Co（2A）-Co（2B）） and 11.5084（3）A × 11.3667（2）A （Co（3）-Co（3C） × Co（4）- Co（4A））, respectively. The phenyl rings are at the comers while the Co（Ⅱ） atoms are in the sides of the grids, and lattice water molecules decorate between the layers. Hydrogen bonds between the layers and lattice water molecules result in the final 3D framework.

A Three-dimensional Supramolecular Complex {[Co(H_2btec)(2,2'-bipy)(H_2O)_3]·H_2O}_n Assembled via Hydrogen Bonding and π-π Stacking Interactions

A new cobalt compound,{[Co（H2btec）（2,2＇-bipy）（H2O）3]·H2O}n （1,H4btec=1,2,4,5-benzenetetracarboxylic acid,2,2＇-bipy=2,2＇-bipyridine）,has been synthesized and charac-terized by single-crystal X-ray diffraction,elemental analysis,IR and X-ray powder diffraction.The crystal belongs to the triclinic system,space group P1,with a=7.230（3）,b=11.626（5）,c=14.001（6）,α=108.12（0）°,β=95.85（0）°,V=1095.33（157）3,C20H20CoN2O12,Mr=539.31,Z= 2,Dc=1.635 g/cm3,μ=0.855 mm-1,F（000）=554,R=0.0427 and wR=0.1042 for 3883 observed reflections （I 〉 2σ（I））.The title compound features a discrete molecular structure,which is connected with each other through extensive O-H…O hydrogen bonds into an intricate 3D supramolecular network.Additionally,two different patterns of π-π stacking interactions further consolidate the framework.

Transition metal coordination polymers with polycarboxylic acid as bridging ligands:Synthesis and structure characterization of[Fe(μ_(4)-bta)_(0.5)(phen)(OH)]_(n)

A new 2D (two-dimensional) coordination polymer, [Fe(μ4-bta)o.5(phen)(OH)]n (1), has been hydrothermally synthesized with FeCl3 6H2, Na4bta (h4bta = 1,2,4,5-benzentetracarboxylic acid), 1,10-phen (1,10-phenanthroline) and H2O as raw materials. The crystals of the compound belong to monoclinic P21/n space group, a = 1.0129(2) nm, b = 0.9265(2) nm, c = 1.5696(3) nm, β=91.37(3)°V=1.4721(5) nm3,Z=3, final R1=0.0292, wR 2=0.0798 for 2572 [/>2σ(/)] observed reflections. The result of structure determination shows that in the compound each bta ligand is connected with four Fe3, forming a new μ4-coordination mode. Four deprotonated carboxylic groups of bta link to Fe3 ions alternatively through monodentate and bidentate coordination fashion, constructing 2D layer network. The measurement of variable temperature magnetic susceptibility indicates that there exist antiferromagnetic interactions between Fe3 ions in the compound. The TGA spectrum displays relatively fine thermal stability of the compound. In addition, IR and UV-Vis spectra of compound 1 have also been measured.

一维链状配位聚合物｛[C u(H_2bttc)(H_2O)_3]·3H_2O｝_n的非等温反应动力学和晶体结构(英文)

为研究配位聚合物｛[Cu(H2bttc)(H2O)3·]3H2O｝n(H2bttc=1,2,4,5-benzenetetracarboxylate)的热分解机理和非等温反应动力学进行了DSC和TG-DTG热分析。由热分析结果和FTIR光谱推测了其热分解机理;将Kissinger法、Ozawa法、积分法和微分法得到的动力学参数进行比较确定了第一个失重过程最可能的动力学模型函数。配位聚合物的X射线单晶结构分析表明它由[Cu(H2bttc)(H2O)3]n分子链组成,并有客体水分子通过分子间氢键附着在分子链上。这一结构特点与热分析结果相一致。还有一种氢键将分子链连接起来形成二维框架,这一框架在失去配位水和结晶水后到553K开始分解。

两个新颖的三维稀土多羧酸配位聚合物:[Ln(ox)_(0.5)(bta)_(0.5)(H_2O)_2]_n的水热合成、结构和荧光性质

采用水热方法合成两种混合多羧酸稀土配位聚合物[Ln(ox)0.5(bta)0.5(H2O)2]n(Ln=Sm(1),Gd(2))(ox=草酸,bta=1,2,4,5-均苯四甲酸),并通过元素分析、红外光谱、X射线单晶衍射及X射线粉末衍射(PXRD)对配合物进行了表征.结构分析表明,配合物和属同构.混合连接体1,2,4,5-均苯四甲酸和草酸连接相应的稀土金属离子,形成复杂的三维网络结构.此外,还对配合物做了热稳定性和荧光性质的研究.

基于苯四甲酸和双(咪唑基甲基)苯配体的三维Cd-MOF的合成、结构及荧光性质

选择刚性的1,2,4,5-均苯四甲酸(H4L)为主配体,以1,3-双(1H-咪唑-1-基甲基)苯(1,3-bib)为辅助配体,在水热条件下,与过渡金属离子Cd^(2+)配位合成了配合物[Cd(L)_(0.5)(1,3-bib)(H_(2)O)]·H_(2)O(1)。利用元素分析、红外光谱、X射线单晶衍射、热重和X射线粉末衍射对其结构进行了表征,并研究了化合物的荧光性质。结果表明:配合物1属正交晶系,空间群Pbca,a=0.85708(4)nm,b=1.91223(10)nm,c=2.45160(12)nm。配合物1中Cd^(2+)与L^(4-)配体的羧基通过双齿螯合配位,通过1,3-bib连接形成三维网状结构。配合物1具有较强的荧光,其对丙酮溶剂、MnO^(-)_(4)、Hg^(2+)离子有一定的荧光猝灭。

三维Cu(Ⅱ)配合物的合成、结构及性能研究

以氮杂环化合物2-（1H-咪唑-1-甲基）-1H-苯并咪唑（imb）和芳香多羧酸均苯四甲酸（H4btec）为配体,采用溶剂热方法制备了一个结构新颖的配合物[Cu（btec） 0.5（imb）]n（1）. 单晶X射线衍射结果表明,配合物1 是由左螺旋链和右螺旋链彼此连接而成的三维结构,可以简化为4,4,4-连接的三维拓扑结构,其拓扑符号为（3^2·10^3·11）（3^2·10^4）（3^2·10^3·11）. 另外还对配合物1 的红外光谱、粉末X射线衍射图谱、热稳定性以及固态荧光性能进行了研究,进一步验证了Cu（II）离子的存在能淬灭配合物的荧光.

含苯四甲酸的邻菲啰啉铜配合物的合成、晶体结构及电化学性质研究(英文)

本文合成了铜配合物[Cu(phen)2Br](H3BTEC)(1,phen=1,10-phenanthroline,H4BTEC=1,2,4,5-benzenetetracarboxylic acid),并对其进行了元素分析、红外、紫外、单晶衍射、热重和电化学性质等表征。测定结果表明,该配合物晶体属三斜晶系,空间群P1,晶胞参数a=0.971 00(19)nm,b=1.212 0(2)nm,c=1.429 0(3)nm;α=102.21(3)°,β=99.57(3)°,γ=107.64(3)°,V=1.517 74(7)nm3,Z=2,C34H21BrCuN4O8,Mr=757,Dc=1.656 g.cm-3,μ=2.098 mm-1,F(000)=762,S=1.059,最终偏离因子R=0.044 9,wR=0.086 4。该配合物中发现了两种不同类型的一维链。一方面,氢键(C-H…Br)和Br…π堆积作用将[Cu(phen)2Br]+连接成一个一维阳离子链;另外,分子间的O-H…O氢键将均苯四甲酸连成一个双层的一维阴离子链。通过结构中的C-H…O氢键作用及其他弱作用将这两条不同的一维链堆积成一个三维结构。