一种链状磷酸铝骨架化合物的离子热合成与表征

以苯甲酸/氯化胆碱形成的离子型低共熔混合溶剂(DES)作为反应介质,采用离子热合成方法研究了磷酸铝骨架材料的合成规律.结果表明,体系中不添加正丙胺时得到的是一种致密的磷酸铝相,体系中氯化胆碱无法发挥模板作用;当添加适量的正丙胺后,合成出一种已知链状结构的磷酸铝化合物(AIPO_4-PrN),并对样品进行了表征.和体系中的氯化胆碱组分相比,添加的正丙胺具有较强的结构导向作用,在形成AIPO-PrN材料时起到了模板或结构导向作用,而苯甲酸/氯化胆碱形成的DES只是作为离子热反应介质.     

超分子化合物(C12N2H9)2(C12N2H8)[SW12O40]的合成与结构表征

利用水热法合成了超分子化合物（C12N2H9）2（C12N2H8）[SW12O40],通过元素分析和X射线单晶衍射确定了其晶体结构,该晶体为正交晶系,P2（1）2（1）2（1）空间群,晶胞参数为a=12．0168（3）A^。,b=21．0534（6）A^。,c=22．5820（6）A^。,V=5713．1（3）A^。^3,α=β=γ=90°,Z=4,Dc=3．977mg·m^-3,并通过IR和XRD进行了结构表征,采用热重分析研究了晶体的热稳定性。该化合物由邻菲罗林和Keggin结构[SW12O40]^2-阴离子组成,以氢键自组装成超分子结构化合物。     

[Mn(C_8H_4O_4)(C_(12)H_8N_2)]_n的合成、晶体结构及热分析动力学

在水热条件下,合成了配位聚合物[Mn(C8H4O4)(C12H8N2)]n(C8H4O4=间苯二甲酸根,C12H8N2=1,10-菲罗啉),通过X-射线单晶衍射、元素分析、红外、热重分析及荧光光谱对其结构、组成和性质进行了表征。结果表明,[Mn(C8H4O4)(C12H8N2)]n为一维链状结构,间苯二甲酸的羧基氧原子采用双齿和单齿桥连两种配位方式配位于Mn2+离子,荧光光谱显示配合物表现为强烈的荧光性。结合Achar微分法和Coats-Redfern积分法,对[Mn-(C8H4O4)(C12H8N2)]n在不同阶段的热分解反应动力学参数E、ln A进行了计算。     

镍卟啉配合物[Ni(bpy)(t-BuOPTPP)]的合成与表征

报道了一种新型尾式卟啉化合物5-(4-叔丁氧基苯基)-10、15、20-三苯基卟啉[H2(t-BuPTPP)]及其Ni(bpy)^2 配合物的合成,并通过元素分析、红外光谱、核磁共振氢谱及紫外可见光谱等对其结构进行了表征。     

化合物[Co(2,2'-bpy)2H2O]12[Mo12V6O42(VO4)][Mo8V8O40(VO4)]3·8H2O的水热合成与晶体结构

用中温水热法合成出一种新的α-Keggin结构化合物[Co(2,2'-bpy)2H2O]12[Mo12V6O42(VO4)][Mo8V8O40(VO4)]3·8H2O,并对其进行了元素分析、IR谱、TGA及X-射线单晶衍射等系列表征.该簇合物属三斜晶系,空间群P-1,a=1.57287(2)nm,b=2.46159(3)nm,c=0.52347(3)nm,α=76.6220(3)°,β=92.078°,γ=79.9390(4) °,V=9.1934(2)nm3,Z=2,Dc=4.642 g·cm-3,μ=4.642mm-1,F(000)=12420,R1=0.0751,wR2=0.1964.化合物中基本构筑单元为三种具有α-Keggin结构的聚阴离子簇,簇与簇之间通过配位阳离子[Co(2,2'-bpy)2H2O]2+桥连成三维结构.化合物中包含少见的六帽α-Keggin结构簇单元.并且在同一晶胞中同时存在聚阳离子和聚阴离子.     

超分子化合物(C12H9N2)(ClO4)的合成及晶体结构

合成了超分子化合物(C12H9N2)(ClO4),该化合物晶体属三斜晶系,P1空间群,晶胞参数是:a=0.58033(7)nm,b=0.9874(2)nm,c=1.0630(2)nm,α=93.22(2)°,β=101.41(1)°,γ=98.04(1)°,V=0.5836(2)nm3,Mr=280.66,Dc=1.597g/cm3,Z=2.邻菲咯啉分子中一个N原子被质子化,并和相邻分子的高氯酸根中的O原子形成氢键,相邻的邻菲咯啉分子间通过π-π堆积把化合物扩展为二维超分子结构.     

配合物[Co（C6H4O2N）2（H2O）4]的合成与晶体结构

采用水热法,用氯化钻与异烟酸反应得到了分子式为[Co（C6H4O2N）2（H2O）4]的配合物,通过X-射线单晶衍射研究了其结构。该配合物的晶体属三斜晶系,空间群P-1,晶胞参数a=0．63736（19）nm,b=0．6921（2）nm,c=0．9282（3）nm,α=96．051（3）°,β=104．703（3）°,γ=0．113084（3）°,V=0．35454（18）nm^3,Z=1,Dc=1．757g／cm^2,Mr=375．20,F（000）=193,μ（MoKa）=1．257mm^-1,R1=0．0834,wR2=0．2302[I〉2σ（I）],晶体由具有六配位的畸变八面体结构的两性离子通过氢键和面．面π-π堆积构成。     

有机锡化合物(o-FC6H4CH2)2SnCl2的合成、表征及晶体结构

利用邻氟苄基氯和锡反应,合成了有机锡化合物(o-FC6H4CH2)2SnCl2。通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体和分子结构。化合物晶体为单斜晶系,空间群C2/c,a=23.794(17),b=4.85(2),c=12.744(9),β=93.880(10)°,V=1467.8(18)3,Z=4,Dc=1.845Mg/m3,μ=2.109mm-1,R=0.0255,wR=0.0738。锡原子呈畸变四面体构型。通过化合物分子间Sn…Cl作用,形成一维链状结构。     

2-[4-(3-甲基-1-咪唑)]苯基丙二腈类两性离子化合物的合成及结构表征

以4-碘苯胺为基础,通过氨基引入咪唑环,再通过卤素碘引入丙二氰,合成了一种新型的2-[4-(3-甲基-1-咪唑)]苯基丙二腈类两性离子化合物,其结构经1H NMR表征,性质经紫外光谱分析,结果表明该化合物具有优良的光学透过性。     

有机锡化合物{n-Bu2Sn[2,6-(O2C)2C5H3N](H2O)}2的合成和晶体结构

利用二丁基氧化锡与2,6-吡啶二甲酸反应合成了目标化合物{n-Bu2Sn[2,6-(O2C)2C5H3N](H2O)}2。用元素分析、红外光谱、核磁共振氢谱以及X-射线单晶衍射进行了表征和结构测定。X-射线单晶衍射测定表明,该化合物为四方晶系,空间群P4(2)/n,a=1.7721(5)nm,b=1.7721(5)nm,c=1.1164(4)nm,α=β=γ=90,°Z=4,V=3.5060nm3,F(000)=1680,R1=0.0344,wR2=0.0853。化合物中两个锡原子呈七配位畸变五角双锥构型。     

配合物Pd(C4H2O4)(C4H8N2)0.5的合成及对苯酚的氧化羰基化的催化活性

A novel complex Pd(C4H2O4)(C4H8N2)0.5 has been synthesized by solvent thermal synthesis and used as a heterogeneous catalyst for direct synthesis of diphenyl carbonate (DPC) by oxidative carbonylation of phenol. In the reaction system of Pd(C4H2O4)(C4H8N2)0.5/Cu(OAc)2/ tetrabutylammonium bromide/ hydroquinone/ 4A molecular sieves, the effect of reaction temperature, time and CO pressure on catalytic activity were investigated, and the results revealed that the catalyst could catalyze oxidative carbonylation of phenol effectively. Under suitable reaction conditions of T=90℃, t=4h, p(O2)=0.3 MPa, p(CO)=3.9 MPa and CH2Cl2 as solvent, the turnover number (TON) of diphenyl carbonate can reach about 13.50 (mol-DPC/mol-Pd), which is higher than the TON for pure PdCl2 under the same reaction conditions.     

Copper(II) azide complexes of [Cu(acac)(N3)(dpyam)] and [Cu(μ-N3-κN1)(C2N3-κN1)(dpyam)]2: Synthesis,crystal structure and magnetism

Two new compounds, [Cu(acac)(N₃)(dpyam)] (1), (acac = acetylacetonate; dpyam = di-2-pyridylamine) and [Cu(μ-N₃-κ^N1)(C₂N₃- κ^N1) (dpyam)]₂ (2), have been synthesized and characterized by single-crystal X-ray diffraction and magnetic analyses. Compound 1 is a mononuclear compound in which each of two independent Cu(II) ions is penta-coordinated with a distorted square pyramidal geometry with distortion parameters τ = 0.21 and 0.16. In contrast, compound 2 is an azido-bridged dinuclear compound with monodentate dicyanamide anions and the Cu(II) ions display a distorted trigonal bipyramidal geometry with τ = 0.73 and end-on azido bridges providing an equatorial–axial position between the metal ions. The EPR spectra of powdered samples for 1 and 2 have also been investigated. Magnetic susceptibility measurements of compound 2 reveal a very weak ferromagnetic interaction between the Cu(II) ions with a J value of +5.8 cm⁻¹.     

A 2D Cu(I) triazolate coordination polymer: Synthesis and characterization of [Cu4Br4(C8H8N4)2]·H2O

The title compound, [Cu₄Br₄L₂]·H₂O (1), (L = C₈H₈N₄, 4-(4-aminophenyl)-4H-1,2,4-triazole) was synthesized from a hydrothermal reaction and characterized by single-crystal X-ray diffraction analysis, IR, and fluorescent spectroscopy. The structure of 1 shows a two-dimensional rectangular grid layer, which is formed by the interconnection of Cu₄Br₄ step-like and the tris(monodentate) L bridges, with guest water molecules filling in the grid. Compound 1 in the solid state exhibits deep green emission with maximum at 538 nm.     

A new hybrid zinc phosphite with a pillared layered structure: Synthesis and characterization of [C6N2O2H16][Zn(HPO3)]2

By using flexible 1,2-bis(2-aminoethoxy)ethane (BAEOE) as a pillaring ligand, a new inorganic–organic hybrid open-framework zinc phosphite, [C₆N₂O₂H₁₆][Zn(HPO₃)]₂ (1), has been hydrothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. The structure of 1 consists of neutral layers of zinc phosphite which are further pillared through linear BAEOE ligands, generating a 3D framework with unusual (3, 4)-connected dmc topology. The participation of left-handed and right-handed helical chains in the construction of puckered sheet structure with 4.8²-net is also noteworthy.     

Synthesis and Structural Characterization of SiO2-Supported PtFe Catalysts Prepared from PtFe2(C8H12)(CO)8

Fourier transform infrared (FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies were used to characterize the species formed following deposition of a PtFe₂(COD)(CO)₈ cluster on SiO₂ and removal of the organic ligands. The results indicate that the PtFe₂(COD)(CO)₈ cluster initially adsorbs weakly on the SiO₂ surface but loses a fraction of the organic ligands during aging under N₂ and thus becomes bonded to the surface. The PtFe₂ cluster core remains nearly intact during this process. The organic ligands can be further removed from freshly impregnated species by thermal treatments in either He or H₂ at 350 °C. Both treatments lead to the formation of bimetallic surface species with average dimensions on the order of 1 nm. However, these PtFe bimetallic species undergo substantial structural changes under CO oxidation conditions.     

酸性离子液体[N4H4(CH2)6].4HSO4催化合成氯乙酸乙酯的研究

以六次甲基四胺和浓硫酸为原料制备了酸性离子液体[N4H4(CH2)6].4HSO4,将其应用到氯乙酸乙酯的合成中,并对酯化反应涉及的工艺参数进行了优化,采用核磁共振波谱对产物进行了表征。结果表明：n（氯乙酸）：n（乙醇）=1:1.8,离子液体用量为氯乙酸总质量的30%,反应温度100℃,反应时间3.5h,氯乙酸乙酯收率为93.27%。重复使用6次,氯乙酸酯收率为90.16%。产品易分离,克服了无机酸催化的缺陷。     

有机模板硼酸盐[C2H8N][B5O6(OH)4]的合成及发光性能研究

以二甲胺和硼酸为原料,通过水热反应合成有机模板硼酸盐[C2H8N][B5O6 (OH)4],通过单晶X射线衍射对其晶体结构进行分析,该晶体属于单斜晶系,空间群为C2/c,晶胞参数为a=1.3381(75) nm,b=1.1468(56)nm,c=1.7137(92) nm,α=90.032(64)°,β=112.292(82)°,γ=89.988(85)°,V=2.433(2.000) nm3.粉末衍射(PXRD),红外(IR),热重(TGA)以及荧光(PL)等手段对其晶体进行分析表征.在不同温度下对该物质进行热处理,观察其IR和PXRD的变化判断其内部的结构是否能够保持稳定,并通过热重分析进行补充说明.荧光光谱结果表明在经过不同温度热处理后,该物质的发光特性发生明显的变化.实验证实[C2H8N] [B5O6(OH)4]一种可能用在白光LED上的荧光粉.