离子液体1-仲丁基-3-甲基咪唑六氟磷酸盐的微波辅助合成、晶体结构及热稳定性

以具有支链结构的溴代仲丁烷作为烷基化试剂, 在微波辐射下采用两步法合成了1-仲丁基-3-甲基咪唑六氟磷酸盐([s-bmim][PF₆])离子液体. 在配比为V(水)∶V(乙醇)∶V(甲苯)=0.16∶2.84∶7的混合溶剂体系中, 培养出晶型完整的长约11 mm的离子液体大单晶体. 通过单晶体X衍射研究了[s-bmim][PF₆]的晶体结构. [s-bmim][PF₆]属于三斜立方晶系, 空间群为P2(1)/m, 晶胞参数为a=0.9042(4) nm, b=0.8213(3) nm, c=0.9775(4) nm, γ=116.618°(6), Z=2, V=64.909(4) nm³, D_c=1.454 g/cm³, μ=0.265 mm^-1, F(000)=292. 在[s-bmim][PF₆]晶体结构中, 阴阳离子间的离子键仍然是主要的, 同时还存在氢键和阳离子-阳离子间的非键斥力作用. 研究结果表明, [s-bmim][PF₆]的支化烷基结构对其晶体有效堆积、熔点、液程范围以及热分解温度等性质具有重要影响.     

Syntheses,Crystal Structures,and Thermal Behaviors of Two New Metallo‐Organically Templated Pentaborates

Two new cadmium borates, [Cd(en)₃][B₅O₆(OH)₄]₂ · 2H₂O (en = ethylenediamine) ( 1 ) and [Cd(DETA)₂][B₅O₆(OH)₄]₂ (DETA = diethylenetriamine) ( 2 ) were synthesized in a novel procedure under mild solvothermal conditions and characterized by single‐crystal X‐ray diffraction, IR spectroscopy, elemental analysis, and TG–DTA. The compound 1 crystallizes in monoclinic system, space group P2₁/c (No. 14) with a = 8.526(2) Å, b = 23.127(6) Å, c = 15.438(4) Å, β = 94.320(3) °, V = 3035.5(13) Å³, Z = 4. Compound 2 is triclinic, space group P$\bar{1}$ (No. 2), a = 8.632(5) Å, b = 9.418(6) Å, c = 27.856(18) Å, α = 95.415(8) °, β = 91.891(7) °, γ = 93.563 (7) °, V = 2248(2) Å³, Z = 3. The anionic units of the both structures, [B₅O₆(OH)₄]^– are linked by hydrogen bonds to form a three‐dimensional framework with large channels, in which the templating cadmium complex cations are located. The thermal decomposition performance of compound 1 requires three steps, whereas only two steps are needed for compound 2 , which all lead to amorphous phases. These processes are well explained considering the structure and the change in the Cd²⁺ coordination during heating.     

室温离子液体电化学稳定性的研究

随着绿色化学的发展,人们对室温离子液体(RTIL)的研究已日益备受重视,较早发现的如由二烷基咪唑正离子(EMI^ )和氯化铝负配离子(A1Cl4^-)组成的离子液体(氯化铝类离子液体),具有许多优良的物理化学性质,如电导率高,在高温下仍有很低的蒸汽压,电化学稳定性好(即有宽阔的电化学窗口),     

Thermal Analysis of Binary Mixtures of Imidazolium,Pyridinium, Pyrrolidinium,and Piperidinium Ionic Liquids

Ionic liquids (ILs) are being widely studied due to their unique properties, which make them potential candidates for conventional solvents. To study whether binary mixtures of pure ionic liquids provide a viable alternative to pure ionic liquids for different applications, in this work, the thermal analysis and molar heat capacities of five equimolar binary mixtures of ionic liquids based on imidazolium, pyridinium, pyrrolidinium, and piperidinium cations with dicyanamide, trifluoromethanesulfonate, and bis(trifluoromethylsulfonyl)imide anions have been performed. Furthermore, two pure ionic liquids based on piperidinium cation have been thermally characterized and the heat capacity of one of them has been measured. The determination and evaluation of both the transition temperatures and the molar heat capacities was carried out using differential scanning calorimetry (DSC). It was observed that the thermal behavior of the mixtures was completely different than the thermal behavior of the pure ionic liquids present, while the molar heat capacities of the binary mixtures were very similar to the value of the average of molar heat capacities of the two pure ionic liquids.     

含氰基离子液体的合成、表征及流变性质研究

摘要合成、 表征了一系列新的含氰基咪唑类离子液体. 测定了该离子液体的密度、 熔点及溶解性等物理性质, 研究了其在稳态、 瞬态和动态条件下的流变行为. 结果表明, 当剪切速率在0.1～50 s^-1范围内时, 其粘度不随剪切速率的变化而变化, 但随温度升高而降低, 粘流活化能随取代基长度变化呈现规律性变化. 对于1-丁基-3-氰乙基咪唑六氟磷酸盐离子液体, 维持剪切速率不变时, 其剪切应力和粘度均不随时间变化, 且随着温度的升高而降低; 在动态条件下, 在线性粘弹区, 复合粘度和损耗模量G″ 随温度升高而降低. 关键词     

Lanthanide Complexes with 2,3‐Dimethoxybenzoic Acid and Terpyridine: Crystal Structures,Thermal Properties,and Antibacterial Activities

The lanthanide coordination complexes Er(2,3‐DMOBA)₃(terpy)(H₂O) ( 1 ) and [Nd(2,3‐DMOBA)₃(terpy)(H₂O)]₂ ( 2 ) (2,3‐DMOBA = 2,3‐dimethoxybenzoate; terpy = 2,2′:6′,2′′‐terpyridine) were synthesized and characterized by IR spectroscopy, powder X‐ray diffraction (XRD), single‐crystal X‐ray diffraction, and thermogravimetric analysis. Complex 1 crystallizes in the triclinic system, space group P1, and the mononuclear subunits form a 1D chain structure along the a axis by hydrogen bonds. Complex 2 crystallizes in the monoclinic system, space group P2₁/c, and the dinuclear subunits are further linked via the offset face‐to‐face π ··· π weak stacking interactions to form a supramolecular 2D layered structure. Thermal analysis showed that the complexes have three decomposition steps. The first step is the loss of coordination water molecules. The neutral terpy ligands and partial 2,3‐DMOBA ligands are lost in the second step. The remaining 2,3‐DMOBA ligands are lost in the third step. The 3D stacked plots for the FT‐IR spectra of the evolved gases are recorded and the gaseous products are identified by the typical IR spectra obtained at different temperatures from the 3D stacked plots. Meanwhile, the results of the antibacterial action tests show that 1 and 2 have better antibacterial activities to Candida albicans than to Escherichia coli or Staphylococcus aureus. In addition, complex 2 has better antibacterial action to Candida albicans than complex 1 .     

Solvent-free Synthesis, Crystal Structure and Thermal Stability of Ionic Liquid 1-Hexadecyl-3-methylimidazolium Bromide

Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate （[C16mim]Br·H2O）, 4 mm in length, was firstly obtained in the water-trichloromethane-toluene growth system （Vwater＇Vtrichloromethane＇Vtoluene = 0.1：1：2）. The crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P1, with a = 5.4962（15）, b = 7.839（2）, c = 27.279（8） A, α = 94.375, β = 91.500, γ = 101.999°, Z = 2, V = 1145.2（5） A3, C20H41BrN2O, Mr = 405.46, Dc = 1.176 Mg/m3, μ = 1.804 mm^-1, F（000） = 436, the final R = 0.0523 and wR = 0.1345. The 3D supramolecular structure is constructed through weak interactions between imidazolium cations, Br- anions and lattice water molecules. The long alkyl chain to the imidazolium ring and lattice water molecules play an important role in the self-assembly process. Moreover, it is proposed that [C16mim]Br in water has aggregation behavior and the possible self-assembled structure is the interdigitated pattern. Finally, thermal stability of [C16mim][Br]·H2O was also studied by DSC and TGA analysis.     

Synthesis and Characterization of Ammonium-, Pyridinium-, and Pyrrolidinium-Based Sulfonamido Functionalized Ionic Liquids

New homologous ammonium-, pyridinium-, and pyrrolidinium-based sulfonamido functionalized ionic liquids have been synthesized in two steps using monoethanolamine, methanesulfonyl chloride, and tosyl chloride as precursors with ethanol as solvent. Attempts to synthesize dual amino functionalized ionic liquid containing both a primary and a secondary amine group in the same ionic liquid are also reported. All functionalized ionic liquids were characterized by ¹H and ¹³C NMR. Melting point and thermal stability of the functionalized ionic liquids were measured by differential scanning calorimetry and thermogravimetric analysis.     

烷基磺酸酯基功能化离子液体的合成、性质及其在酯化反应中的应用(英文)

采用廉价易得的原料合成了阳离子含有烷基磺酸酯官能团的功能化离子液体,并考察了其热稳定性.该离子液体可催化羧酸的酯化反应,其催化活性高于阳离子非功能化的离子液体,而与磺酸功能化离子液体相当.同时采用电喷雾电离质谱考察了该离子液体在酯化反应中的作用.     

两个新的双二茂铁硫脲衍生物FcL1和FcL2的合成、结构及电化学性质

以二茂铁苯甲酰氯和二茂铁间(对)苯胺为原料,合成了两个新的双二茂铁硫脲衍生物FcL₁和FcL₂.通过IR,¹HNMR和元素分析等手段确定了标题化合物的结构.X射线单晶结构分析表明,FcL₁属于三斜晶系,P1空间群,R₁=0.0786,wR=0.1762.电化学分析结果表明,FcL₁和FcL₂的电化学性质相似,说明化合物中的两个二茂铁基所处的化学环境基本相同.间苯胺取代和对苯胺取代对化合物在电极表面的扩散系数影响不大,但对其反应速率常数则有较大的影响.     

功能化苯并咪唑类离子液体的合成及性质

合成了一系列由磺酸基、 羧基修饰的新型功能化苯并咪唑类离子液体, 采用IR, ¹H NMR, ¹³C NMR和ESI-MS对其结构进行了表征, 研究了化合物的热稳定性、 电导率以及室温下在各种溶剂中的溶解性等性质. 结果表明, 该类离子液体在 280 ℃以下基本没有失重, 热稳定性较好; 在水溶液浓度为1×10^-3 mol/L时, 随着温度的升高, 电导率几乎与温度呈正比增大; 能与大多数有机溶剂互溶, 溶解性随着溶剂极性的增加而增大.     

Crystal Structures,Thermal Behavior Analysis and Thermal Safety of Two Energetic Salts of Hydrazinyl-1,2,4,5-tetrazine with 3,5-Dinitrosalicylic Acid

Two energetic salts, DPHT·DNS·H₂O(1) and DHT·2DNS·2H₂O(2)[DPHT=3-(3,5-dimethyl-1H-pyrazol-1-yl)-6-hydrazinyl-1,2,4,5-tetrazine; DHT=3,6-dihydrazinyl-1,2,4,5-tetrazine], were synthesized from S-tetrazine with 3,5-dinitrosalicylic acid(DNS). Compounds 1 and 2 were structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. The thermal behavior of the title compounds was studied by differential scanning calorimetry(DSC) and thermogravimetry(TG). The non-isothermal decomposition kinetics of compound 2 were investigated. The self-accelerating decomposition temperature, thermal ignition temperature, and critical temperatures of thermal explosion were obtained to evaluate the thermal safety of compound 2. The results show compounds 1 and 2 decompose at 150.8 and 179.2℃, respectively. The T_SADT and T_b of compound 2 are higher than those of DHT, which indicates compound 2 is a potential candidate for energetic materials that have good thermal stability.     

（TAGH）2（TNR）的合成、晶体结构及热分析

合成了三氨基胍三硝基间苯二酚盐(TAGH)2(TNR)(TAG)三氨基胍;TNR:2,4,6-三硝基间苯二酚),并对其进行了元素分析及红外光谱表征.利用X射线单晶衍射分析测定了其晶体结构.该晶体属于单斜晶系,空间群为C2/c,晶体学数据为,a=2.2892(6)nm,b=1.2802(3)nm,c=1.3661(4)nm,β=111.174(5)°,V=3.7333(16)nm3,Z=8.该化合物是由二个C(N2H3)3+与一个(C6HN3O8)2相结合而成的离子型化合物.用差示扫描量热法、热重法和微商热重法研究了该化合物的热分解过程,研究结果表明,在10 K·min-1的升温速率下,该化合物只有一个剧烈的放热分解过程,该过程发生在450.1-477.7K之间,且分解产物主要是气体产物.     

聚乙二醇功能化离子液体的制备及其在有机反应中的应用

聚乙二醇功能化离子液体作为一个新的研究方向受到了化学研究者关注,该类离子液体已经成功地应用于许多有机合成反应中,可以明显改善催化剂性能,并可在一定程度上解决传统催化剂使用中遇到的难分离、难回收再利用的问题。本文介绍了聚乙二醇功能化离子液体的发展历程、制备方法和其作为反应介质、溶剂或催化剂在有机合成反应中应用的最新研究成果,主要包括加成反应、缩合反应、还原反应、酯化反应、硝化反应、氧化反应、水解反应、Heck 反应以及Suzuki-Miyaura反应等。     

离子液介质中硫化铋单晶纳米棒制备与表征

采用硝酸铋和硫脲为先驱原料，以离子液为反应介质，合成了硫化铋单晶纳米棒。所得产物用X射线粉末衍射、X射线能量色散谱、透射电子显微镜、高分辨电子显微镜、选区电子衍射、扫描电子显微镜、紫外-可见吸收光谱进行了表征。结果表明，在含有乙基硫酸根离子的1-甲基3-乙基咪唑盐的离子液中，160 ℃下回流反应，可以得到结晶良好的硫化铋纳米棒，并对其形成机理进行了探讨。     

(TAGH)2(TNR)的合成、晶体结构及热分析

合成了三氨基胍三硝基间苯二酚盐(TAGH)2(TNR) (TAG: 三氨基胍; TNR: 2,4,6-三硝基间苯二酚), 并对其进行了元素分析及红外光谱表征. 利用X射线单晶衍射分析测定了其晶体结构. 该晶体属于单斜晶系, 空间群为C2/c, 晶体学数据为, a=2.2892(6) nm, b=1.2802(3) nm, c=1.3661(4) nm, β=111.174(5)°, V=3.7333(16) nm3, Z=8. 该化合物是由二个C(N2H3)+3与一个(C6HN3O8)2-相结合而成的离子型化合物. 用差示扫描量热法、热重法和微商热重法研究了该化合物的热分解过程, 研究结果表明, 在10 K·min-1的升温速率下, 该化合物只有一个剧烈的放热分解过程, 该过程发生在450.1-477.7 K之间, 且分解产物主要是气体产物.     

Syntheses and Crystal Structures of Functionalized Tetramethyl Resorcinarenes

Tetramethyl resorcinarene, which was obtained by acidic condensation of resorcinol with paraacetoaldehyde, was chemically modified to the functionalized O-acyl, O-tosyl and O-acetate derivatives by corresponding acylation, p-toluenesulfonylation and alkylation reactions. The single crystal structures of these functionalized resorcinarenes and the complex of tetramethyl resorcinarene with 2,2'-bipyridine were determined by X-ray diffraction method. All these resorcinarenes adopt the all-cis configuration with four methyl groups stretching to the down rim and form 1D or 2D structures through H-bonds.     

Synthesis, Crystal Structure and Thermal Analysis of (TAGH)2(TNR)

A new energetic compound (TAGH)₂(TNR) (TAG: triaminoguanidine, TNR: 2,4,6-trinitroresorcinol) was prepared by reacting triaminoguanidine with 2,4,6-trinitroresorcinol (styphnic acid) in aqueous solution under nitrogen atmosphere, and characterized by elemental analysis and Fourier transform infrared (FTIR) spectra. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belonged to a monoclinic, C 2/c space group. The unit cell parameters were as follows: a=2.2892(6) nm, b=1.2802(3) nm, c=1.3661(4) nm, β=111.174(5)°, V=3.7333(16) nm³, and Z=8. The compound consisted of two cations C(N₂H₃)₃⁺ and an anion (C₆HN₃O₈)²⁻. The C(N₂H₃)₃⁺ and (C₆HN₃O₈)²⁻ were bonded together by electrostatic attraction and hydrogen bonds, and this effect made the compound more stable. The thermal analysis of the compound was studied by using differential scanning calorimetry (DSC), thermogravimetry-derivative thermogravimetry (TG-DTG). Under nitrogen atmosphere with a heating rate of 10 K·min⁻¹, the thermal decomposition of the compound contained only one intense exothermic decomposition process in the range of 450.1-477.7 K in the DSC curve, and the decomposition products were nearly gaseous products.     

辣根过氧化物酶在亲水性离子液体中的活性与稳定性研究

基于辣根过氧化物酶对过氧化氢氧化愈创木酚这个显色反应的催化作用,研究了辣根过氧化物酶在七种亲水性离子液体[C2mim][BF4]、[C4mim][BF4]、[C6mim][BF4]、[C4mim]HSO4、[C4mim]Cl、[C4mim]NO3、[C4mim][CF3CO2]中的活性与稳定性变化.结果表明辣根过氧化物酶在不同离子液体中均有不同程度的失活,辣根过氧化物酶活性随离子液体极性增强而降低.辣根过氧化物酶在含[C4mim]Cl离子液体的介质中,随着温度升高,[C4mim]Cl对辣根过氧化物酶的失活过程起加速作用,离子液体浓度越高,酶的热稳定性越差.紫外-可见光谱研究表明,在含[Cnmim][BF4]、[C4mim]HSO4、[C4mim]Cl、[C4mim]NO3的介质中,辣根过氧化物酶血红素中心最大吸收峰没有发生变化,但吸收值增强,证明离子液体使酶的血红素基团暴露于介质中而增强了吸收;而在含[C4mim][CF3CO2]的介质中,辣根过氧化物酶血红素基团最大吸收峰区发生蓝移,证明有部分血红素基团被离子液体破坏而脱落.     

1-烷基-3-甲基咪唑系列室温离子液体表面张力的研究

合成了系列1-烷基-3-甲基咪唑四氟硼酸盐([C_2～7mim]BF₄)及六氟磷酸盐([C_4～7mim]PF₆)室温离子液体, 并通过核磁氢谱、红外光谱、质谱等手段对其进行了结构表征; 采用Wilhelmy白金板法, 在293～338 K范围内测定了离子液体的表面张力, 测试结果显示, 同类离子液体表面张力γ随温度的升高而线性下降, 同种离子液体的表面张力呈现出较宽的变化范围, 如293 K下, 表面张力值从[C₂mim]BF₄的50.4 mJ/m²到[C₇mim]BF₄的36.1 mJ/m². 最后对离子液体的表面性能进行了讨论.