Syntheses, Crystal Structure and Luminescent Properties of a Novel Mn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylic Acid

Coordination polymers are a novel class of crystalline materials, which have attracted a huge amount of interest in recent decades. We selected an organic ligand 1,3,5-benzenetricarboxylic acid（H_3 BTC） to assemble with Mn（Ⅱ） ions to construct a novel Mn（Ⅱ） coordination polymer crystal material（namely complex 1）. The resultant sample was successfully synthesized under the solvothermal reaction. Complex 1 possesses a three-dimensional（3D） framework based on two different Mn（Ⅱ） clusters： [Mn_4（COO）_8] and [Mn_2（COO_4）]. Furthermore, the resultant sample can be characterized in detail by powder X-ray diffraction（PXRD）, Fourier-transform infrared spectra（FT-IR）, thermal gravimetric analyses（TGA）, elemental analysis（C, H and N） and luminescence.

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn（Hbtc）（bpyb）]·H2O}n（1） and {[Cd（Hbtc）-（bpyb）（1.5）]·0.5 bpyb}n（2）（H3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis（4-pyridyl）benzene） have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H…N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H…N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.

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.

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.

Crystal Structure of a Novel Complex Na_4[Y(PDC)_2(BTC)]·5H_2O with One-Dimensional Helical Network Structure (H2PDC = 2,6-Pyridinedicarboxylic acid)( H_3BTC = 1,3,5-Benzenetricarboxylic acid )

A novel title complex, C23H19N2O19Na4Y （Mr= 808.27）, has been synthesized by hydrothermal reaction and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 13.560（3）, b = 14.016（3）, c = 14.948（4） A, β = 99.492（4）°, Z = 4, V = 2802.2（12） A^3, Dc = 1.916 g/cm^3,μ（MoKα） = 2.241 mm^-1, F（000） = 1624, the final R = 0.0337 and wR = 0.0828 for 4044 observed reflections（I〉 2σ（I））. In the crystal, each eight- coordinated Y（Ⅲ） atom is linked by carboxyl groups of BTC to form a one-dimensional helical network structure.

Hydrothermal Syntheses and Crystal Structures of Cd(Ⅱ) and Cu(Ⅱ) Complexes Constructed with 1,3,5-Benzenetricarboxylic Acid and Dipyrido[3,2-a:2?,3?-c]phenazine Ligands

Two novel coordination compounds, [Cd2（HBTC）2（DPPZ）2（H2O）3].2H2O （1） and [Cu2（HBTC）2（DPPZ）2（HEO）]n （2） based on 1,3,5-benzenetricarboxylic acid （H3BTC） and dipyrido[3,2-a：2＇,3＇-c]phenazine （DPPZ） ligands, have been constructed under hydrothermal conditions. Two complexes are characterized by elemental analysis, IR and single-crystal X-ray diffraction. Structural analyses show that both complexes 1 and 2 present the three-dimensional supramolecular structures. In addition, two complexes exhibit luminescence property.

Synthesis,Crystal Structure and Properties of Barium Coordination Compound Based on 1,3,5-Benzenetricarboxylic Acid Ligand

A new coordination polymer [Ba3（btc）2（H20）s]·2H20 （1, H3btc = 1,3,5-benzenetri- carboxylic acid） has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis and infrared spectroscopy analysis. All carboxylate oxygen atoms of btc3- participate in coordination with the central Ba（II） ions. The Ba（1） center is eight-coordinated with a distorted square antiprismatic coordination geometry, while the Ba（2） ion is ten-coordinated with a distorted dicapped square prism. Three carboxyl groups of the anion btc3 take μ2-η1：η1and μ2-η2 ：η2 coordination modes, respectively. The whole btc3 anion acts as a μ6-bridge connecting six different Ba（Ⅱ） ions to form a 3D framework structure. Luminescent and thermal stable properties of complex 1 were investigated.

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.

Synthesis, Structure and Luminescent Property of a New Zn(Ⅱ) Coordination Polymer Based on 1,3,5-Benzenetricarboxylate and 4,4'-Bipyridine Ligands

A new Zn（II） coordination polymer [Zn3（BTC）2（4,4＇-bpy）（CO）2]n （1, H3BTC = 1,3,5-benzenetricarboxylic acid, 4,4＇-bpy = 4,4＇-bipyridine） has been prepared through urothermal reaction of zinc nitrate hexahydrate with 1,3,5-benzenetricarboxylic acid and 4,4＇-bipyridine, and characterized by elemental analysis, IR spectroscopy, TGA and powder XRD, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in the monoclinic system, space group C2/c, with a = 10.262（3）, b = 18.838（5）, c = 15.083（4）/k, fl = 99.203（4）°, V = 2878.3（14） A3, C30H14Zn3N2O14, Mr= 822.54, Z = 4, Dc = 1.898 g/cm3,μ = 2.561 mm-1,F（000） = 1640, R = 0.0363 and wR = 0.0932 for 2828 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn（lI） atoms which are connected by BTC3- ligands and 4,4＇-bpy coligands to form a 3D framework with 1D channels. The solid luminescence of ligand and the title complex was also studied at room temperature.

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.

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.

1,3,5-苯三甲酸衍生物类新型成核剂的合成及应用研究

合成了新型成核剂1,3,5-苯三甲酸三(环己胺)(BTCA-TCHA),研究了该成核剂对等规聚丙烯力学性能、结晶行为和熔融行为的影响。结果表明,成核剂BTCA-TCHA可明显改善等规聚丙烯的力学性能和光学性能,并可以大幅度提高结晶峰温度。当BTCA-TCHA添加量为0.2%时,等规聚丙烯的拉伸强度和弯曲模量可分别提高9.72%和12.4%,雾度降低53.5%。当降温速率为20℃/min时,添加BTCA-TCHA的等规聚丙烯的结晶峰温度可从空白样的114.6℃提高到126.8℃。BTCA-TCHA的性能与传统的山梨醇类成核剂Millad 3988基本接近。

异丁醛合成2,4,6-三异丙基-1,3,5-三噁烷的研究

本文以异丁醛为原料在杂多酸催化剂的作用下 ,环化合成了无毒升华剂 2 ,4 ,6 -三异丙基 -1,3,5 -三烷 ,考查了各种反应条件的影响 ,确定以磷钨酸为催化剂时的最佳反应条件 :反应温度 2 5℃ ,催化剂用量 1 5 % ,反应时间 2 5h ,产物的收率达 84

三聚氰酸为基的2,4,6-三氧-[1,3,5]三嗪烷-1-三氨基胍盐的合成、晶体结构和热性能（英文）

以三聚氰酸钠(CANa)和三氨基胍盐酸盐(TAG-HCl)为原料,通过一步复分解反应制备了一种富氮含能化合物——2,4,6-三氧-[1,3,5]三嗪烷-1-三氨基胍盐(1),收率91%。采用X-射线单晶衍射、UV-Vis、FTIR、~1H NMR以及元素分析等对产物进行了结构表征。计算了产物的生成焓和爆轰参数。通过差示扫描量热法(DSC,10 K·min^(-1))和热重-傅里叶变换红外光谱联用分析了其热稳定性、非等温热分解动力学和热分解过程。通过落锤法测试了产物的撞击感度。结果表明,化合物1的晶体为单斜晶系,P2_1/n空间群,计算密度为1.676 g·cm^(-3),生成焓为327.9 kJ·mol^(-1),爆速为7900 m·s^(-1),爆压为26.5 GPa。化合物具1有良好的热稳定性,分解峰值温度为538.9 K,提出了N_2气氛下可能的热分解机理。且化合物1对撞击非常钝感,撞击感度大于60 J,优于TATB(50 J)。

D,L-乳酸-1,3,5-苯三氧乙酸共聚物的合成与表征

为了研究聚乳酸(PLA)在长效农药缓释方面的应用,以D,L-乳酸和植物生长调节剂1,3,5-苯三氧乙酸为原料,采用工艺简单、成本低廉的直接熔融聚合法合成了可生物降解的D,L-乳酸-1,3,5-苯三氧乙酸共聚物。用1HNMR、GPC、XRD、IR、DSC、特性黏度等手段对聚合物的结构与性能进行了表征。所得共聚物的重均分子量Mw可达到3000以上,玻璃化温度为10.56℃,熔点为118.0℃,有望应用于农药缓释领域。

1,3,5-三芳基苯的合成及研究进展

1,3,5-三芳基苯因其特殊对称结构以及卓越的光、电、磁特性,被广泛应用于构筑树枝状大分子和各种聚苯化合物的核芯模块。本文主要介绍了1,3,5-三芳基苯合成方法的发展近况,以及几种有代表性的合成方法。

微波辐射合成1,3,5-苯三氧乙酸的研究

在微波辐射下,以1,3,5-苯三酚、氯乙酸和氢氧化钠为原料合成了1,3,5-苯三氧乙酸,考察了反应物的摩尔比、微波功率、辐射时间等因素对反应收率的影响。结果表明,当1,3,5-苯三酚、氯乙酸和氢氧化钠的摩尔比为1∶3.4∶5.0,微波功率为400 W,辐射时间为8 min时,1,3,5-苯三氧乙酸的收率为78.3%。

2,4,6-三(4-羧基-1-羧丙氨基)-1,3,5-三嗪的合成及阻垢性能

用三聚氯氰和谷氨酸为原料,合成2,4,6-三(4-羧基-1-羧丙氨基)-1,3,5-三嗪(TGAT)。讨论了反应物配比、反应时间、反应温度对产率的影响。FTIR及1HNMR表征了衍生物的结构。通过对产物进行阻垢实验发现,该类型阻垢剂对碳酸钙有良好的阻垢效果。通过扫描电镜考察了阻垢剂碳酸钙垢晶形的变化,结果表明,TGAT可使碳酸钙垢晶形完全扭曲,形成球霰石晶体,从而达到阻垢目的。

N,N'-二-(4,6-二氯-[1,3,5]-三嗪基)-2,6-二氨基己酸的合成与鞣制性能

在水为介质的条件下,以三聚氯氰(TCT)与赖氨酸(Lys)为原料,经缩合反应制备N,N?-二-(4,6-二氯-[1,3,5]-三嗪基)-2,6-二氨基己酸(简称DTDHA),利用FTIR和1HNMR对其结构进行了表征。通过正交实验考察了原料物质的量之比、缚酸剂种类、反应时间对产物收率的影响,得出较适宜的反应条件为:n(三聚氯氰)∶n(赖氨酸)=3.0∶1.0,KOH做缚酸剂,反应时间6 h,在该条件下DTDHA产率为91%。并将产物应用于生皮鞣制,以鞣制坯革的收缩温度为考察指标,采用单因素实验对鞣制工艺条件进行了优化。得到适宜的鞣制工艺条件为:鞣剂用量20%(以灰皮质量为基准,下同),温度从25℃开始每隔2 h阶梯上升15℃,最终达到55℃,鞣制总时间8h,在该条件下,坯革的收缩温度为85.6℃。该鞣制工艺下合成产物具有良好的鞣制效应,是一种新型的有机合成鞣剂。

对-(4,6-二氯-1,3,5-三嗪-2-氧基)苯磺酸钠的合成及其鞣革性能

以水为溶剂,采用三聚氯氰与4-羟基苯磺酸缩合一步法制得对-(4,6-二氯-1,3,5-三嗪-2-氧基)苯磺酸钠(简称TSP),利用FTIR、1HNMR对其分子结构进行了表征。以鞣后坯革的收缩温度及物理感官作为评价鞣制效果的依据,通过单因素实验得到合理的鞣制条件:鞣剂TSP用量25%(以绵羊灰皮质量计,下同),鞣制温度以25、40、50℃阶梯上升,每个温度鞣制2h,鞣制总时间为6h,通过提碱使浴液pH最终维持在5.5~6.0。实验结果表明:TSP鞣制的坯革收缩温度可达78.4℃,粒面平细,抗张强度为14.15 N/mm^2,撕裂强度为36.44 N/mm,规定负荷10 N/mm^2下伸长率为25.58%。