磷酸铍微孔晶体的合成与表征

近年来,非硅铝骨架原子构成微孔晶体的开发研究受到极大的重视。铍与磷原子均可形成稳定的四面体单元,这是构成微孔骨架晶体的最佳配位态。磷原子作为骨架原子的可能性已被证实并得到广泛的研究。但铍原子的利用却少有报道。我们采用水热晶化法合成出五种磷酸铍微孔晶体,命名为BePO_4-CJ_n(n=8-12)(C代表China,J代表吉林大学),并进     

无机微孔材料磷酸镍的合成与表征

在水热条件下，合成了三种新型磷酸镍无机微孔材料，通过ICP、CHN元素分析、EDX确定了成分，对其进行了红外光谱、XRD粉末衍射结构表征，用SEM观察了它们的形貌，通过TG-DTA和TG-DSC分析了它们的热稳定性。     

四面体磷酸镓和磷酸锗镓构成的新型—维链状分子筛结构

以1，3-丙二胺为模板剂，在溶剂热条件下合成了两个一维磷酸盐微孔分子筛 ：[GaP2O7(OH)][NH3(CH2)3NH3](1)和[Ge0.5GaP1.5O6.5(OH)1.5][NH3(CH2)3NH3] (2).X射线单晶结构解析表明，两个晶体结构分别由镓氧四面体和磷氧四面体，或 镓氧四面体，锗氧四面体和磷氧四面体组成，并沿层c轴方向形成链，这些链之间 由1，3-丙二胺相连，1的结晶学数据为Mr=331.82,P-1,a=0.8303(2)nm,b=0.8614 (3)nm,c=0.8880(2)nm,a=111.70(3)°,β=107.5(92)°,γ=98.39(2)°，V=0. 5382(3)nm^3,Z=1,MoKa,λ=0.071073nm,R(F)=5.56,wR(F^2)=14.36,2的结晶学数据 为：P2（1）/c,a=0.88968(7)nm,b=1.67562(13)nm,c=0.83666(7)nm,β=115.890 (2),V=1.12208(16)nm^3,Z=4,MoKa,R(F)=4.66,wR(F2)=10.10。     

一种新型磷酸铍微孔晶体的合成与表征

水热晶化法合成并培养一种新型磷酸铍微孔晶体。经多晶X射线衍射, 四圆X射线单晶结构分析, 红外光谱等测定, 其骨架结构是由磷氧四面体和铍氧四面体交替的, 通过共用顶点氧原子(氧桥形式)构成的阴离子骨架。晶体属正交晶系,空间群为Pna21, 晶胞参数a=0.8699(1)nm, b=0.856(1)nm, c=0.4953(2)nm, 晶胞体积V=0.3691(7)nm^3。Z=4, 求解结构中最后R=0.054, Rw=0.048。微孔体系由4,6和8元环组成。水分子和平衡阴离子骨架电荷的质子位于平行(100)方向的六元环通道中, 研究其热稳定性能。     

镨与磷酸二甲酯配合物的合成与结构研究

合成了镨与磷酸二甲酯的配合物,元素分析表明配合物分子式为Pr[(CH_3O)_2PO_2]_3。测量了它的红外和拉曼光谱。用X射线单晶衍射法测定配合物空间群为这P,a=1.8747 (3),b=1.1050 (2),c=1.8010 (3) nm;α=105.42 (1)°,β=98.80 (1)°,γ=79.41 (1)°;ν=3.509(0)nm~3,z=8。镨与六个氧原子配位,每两个相邻的镨原子之间通过双“O-P-O”桥连结;形成奇特的“双桥二十四元环”的环套环绸状结构。     

Dawson结构钼磷酸的合成与表征

合成了H_6P_2Mo_(18)O_(62)杂多酸及其四丁基铵盐和四丁基鏻盐,用IR、~(31)P NMR、GV等手段核查其纯度并研究了热稳定性、酸性和氧化还原性。结果表明,Dawson结构钼磷酸较Keggin结构钼磷酸有更强的氧化性。     

乙二胺导向合成的微孔晶体磷酸钴的转化现象

以乙二胺为模板剂(SDA)合成微孔晶体磷酸钴, 可以得到多种不同的结构. 本文在合成四种不同结构类型的微孔磷酸钴(命名为CoPO-en-1, CoPO-en-2, CoPO-en-3, CoPO-en-4, en 为乙二胺的英文缩写)过程中发现, 它们之间不仅可以在水热合成条件下相互转化, 在焙烧处理条件下也能实现转化. 研究发现, 在水热合成过程中, CoPO-en-2、CoPO-en-4 分别是CoPO-en-1、CoPO-en-3 的晶化中间物, 在较低晶化温度下或者较高温度的晶化初期, 可以发现它们的身影. 一旦晶化温度升高或者晶化时间延长, 它们就分别转化为CoPO-en-1和CoPO-en-3. 在合成产物的热处理过程中发现: CoPO-en-2、CoPO-en-3、CoPO-en-4 都能够通过焙烧转化为CoPO-en-1. 这种现象表明, 几种微孔磷酸钴结构间的稳定性存在递变关系.     

微孔纳米羟基磷灰石的水热合成与结构表征

以Ca(NO3)2.4H2O,P2O5为原料,水-乙醇体系为溶剂,在碱性介质中,采用水热法合成微孔羟基磷灰石,并考察了水热温度、时间对晶体结构的影响。通过X-射线衍射(XRD)、红外光谱(FTIR)、热分析(TG/DTA)、透射电镜(TEM)等检测手段对HAP的晶相、化学组成和形貌进行了表征和分析,结果表明:160℃下水热8小时,可得到粒径为70×167nm的六方柱状微孔纳米HAP晶体,晶体表面孔径大约为1~2nm,孔密度大约为3×109个/cm2。     

镓取代皂石的合成与交联的研究

以XRD、MAS NMR、IR和化学分析等方法研究了镓取代皂石及其羟基铝低聚物交联物。结果表明,Ga占据骨架四面体位置,影响四面体层电荷及Al柱的交联密度。交联物经焙烧后,Al柱与层形成Ga—O—Al_p键,实现了层与柱的交联,而Al_(13)基本结构不变。     

磷酸铕钠及其与磷酸钡钠的固溶体的合成、结构与性质的研究

用钠蒸气还原ＥｕＰＯ４合成了新化合物ＮａＥｕＰＯ４其结构属三方晶系．空间群Ｐ３ｍｌ，ａ＝５４９．９（２），ｃ＝６９６．１（２）ｐｍ，Ｚ＝２，Ｄｘ＝４．９１７ｇ·ｃｍ（－３），Ｇｌａｓｅｒｉｔｅ（ＫＮａＳＯ４）晶型．在晶体中铕（Ⅱ）和钠离子有序地分布在四个Ｃ（３Ｖ）格位上，具双中心荧光发射３８９．２，４６５．６ｎｍ．它与ＮａＢａＰＯ４可形成无限固溶体并且有很强的荧光．还报道了红外图谱．     

An Isoreticular Family of Microporous Metal-Organic Frameworks Based on Zinc and 2-Substituted Imidazolate-4-amide-5-imidate: Syntheses, Structures and Properties

We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1-4, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0-1.7??), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and (1) H?MAS and (13) C?CP-MAS?NMR spectroscopy. All IFPs showed high thermal stability (345-400?°C); IFP-1 and IFP-4 were stable in boiling water for 7?d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO(2) was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH(4) (at 298?K), CO(2) (at 298?K) and H(2) (at 77?K) at high pressure were also investigated. In situ IR spectroscopy showed that CO(2) is physisorbed on IFP-1-4 under dry conditions and that both CO(2) and H(2) O are physisorbed on IFP-1 under moist conditions.     

二个新颖的一维聚合物{(PyH)3[Cu3Br6]}∞和{(γ-MePyH)2[Cu2Br4]}∞的合成和晶体结构

Reactions of CuBr with equimolar PyHBr or γ-MePyHBr afforded two novel one-dimensional bromocuprate(Ⅰ)polymers {(PyH)₃[Cu₃Br₆]}_∞ (1) and {(γ-MePyH)₂[Cu₂Br₄]}_∞(2)， respectively. Both 1 and 2 were charac-terized by IR， elemental analysis， and X-ray crystallography. Crystal data for 1: monoclinic， space group P2₁/n， a=0.93262(12)nm， b=1.3497(2)nm， c=1.9149(2)nm， β=93.465(7)°， V=2.4060(5)nm³， Z=4. Crystal data for 2: orthorhombic， space group Pbcm， a=0.8659(4)nm， b=1.5669(6)nm， c=1.2849(5)nm， V=1.7432(2)nm³， Z=4. The structure of 1 has a unique helical chain composed of [Cu₃Br₅] units and μ-bromide anions while that of 2 shows a linear chain consisted of [Cu₂(μ-Br)₂] units bridged by pairs of μ-Br atoms. CCDC: 1， 208412; 2， 208413.     

Syntheses and Crystal Structures of Three Novel Amino-acid-containing Polyoxomolybdosilicates

1 INTRODUCTION Polyoxometalates as metal-oxygen cluster ions have received a great deal of research due to their potential applications in catalysis, medicine and ma- terials science[1]. The modification of organic groups to the surface of polyoxoanions gives POMs more interesting character, and many derivatives of poly- oxoanions with organic ligands have been studied[2]. Particularly the potential applications of polyoxo- metalate as drugs in anti-viral and anti-AIDS have attracted t…     

一类六核三价铁簇化合物的合成及结构表征

选择3种不同尺寸含氮配体（哌嗪、咪唑和三氮唑）与三羟甲基丙烷（H₃tmp）和FeCl₃采用溶剂热反应合成3例六核Fe（Ⅲ）合物：（C₅H₁₄N₂）[Fe₆（μ₆-O）Cl₆（tmp）₄]·2H₂O·CH₃OH （1）、（C₃H₅N₂）₂[Fe₆（μ₆-O）Cl₆（tmp）₄] （2）和（C₄H₈N₃）₃（C₂H₄N₃）[Fe12（μ₆-O）₂Cl₁₂（tmp）₈]·3CH₃OH （3）,并对它们的结构进行表征。发现三元醇配体有利于合成高核金属簇。3个化合物具有相同的阴离子簇[Fe₆（μ₆-O）Cl₆（tmp）₄]^2-。通过晶体学参数,元素分析,红外等手段证实,在化合物1和3的体系中,氮杂环配体经历了N-和C-烷基化反应。     

Syntheses,Crystal Structures and Theoretical Studies of Three Novel Salts of Vortioxetine and the Investigation of Their Solubility

Three new vortioxexine(VOT) salts with salicylic acid(SA), 5-fluorouracil(FU) and(p-nitrophenyl)-acetic acid(PA) have been synthesized and characterized in detail. In VOT-SA(1:1), the protonated VOT and deprotonated salicylic anion form a tetrameric unit with the R4 4(12) synthon via N(1)–H(1)···O(1)a(a: x–1, y, z) and N(1)–H(2)···O(2)b(b: –x, –y, –z+1) hydrogen bonds. However, in VOT–FU(1:2), the protonated VOT and deprotonated 5-fluorouracil anion feature an R4 4(16) ring motif via N(1)–H(1)···O(2)c(c: –x+1, –y+1, –z+1) and N(1)– H(2)···O(1)d(d: x, y–1, z) hydrogen bonds. The neutral FU extends the R4 4(16) ring to form a two-dimensional structure through R2 2(8) N–H···O and N(6)–H(4)···N(4)e(e: –x+1, y–1/2, –z+1/2) hydrogen bonds. In VOT-PA(1:1), PA molecules are linked through N(1)–H(1)···O(1)f(f: –x+1, y+1/2, –z+1) and N(1)–H(2)···O(2), which forms a right-handed helical structure. Furthermore, components of the crystalline phase have also been investigated in terms of their corresponding Hirshfeld surface, and the salification improves the equilibrium solubilities and dissolution rates of VOT in three salts at 25 ℃ in water.     

两个新型锌的配位聚合物的合成与晶体结构

本文以Zn(NO3)2.6H2O分别与1,3,5-均苯三甲酸(1,3,5-H3BTC)和2,5-噻吩二羧酸(2,5-H2TDC)通过水热/溶剂热反应合成了2个锌的配位聚合物[Zn3(OH)(BTC)2(C4N2H11)(H2O)]n(1)(C4N2H11=质子化的哌嗪)和[Zn(2,5-TDC)(i-PrOH)]n(2)。并对配位聚合物1和2进行了元素分析、FTIR和X-射线单晶结构解析等表征。X-射线单晶结构解析表明配位聚合物1和2的晶体均属于正交晶系,空间群分别为Pbca和P212121。化合物1中含有Zn3O结构单元,Zn3O结构单元通过BTC的连接构成1个层状结构,层状结构再通过堆积形成1个三维结构。化合物2中含有无机的Zn-O链。无机Zn-O链通过TDC配体与相邻的6个无机Zn-O链相连形成三维开放式的框架结构。     

Syntheses and Structures of Two Novel Salicylate-containing Mononuclear Manganese Complexes

Two salicylate containing mononuclear manganese complexes formulated as [Mn- (sal)2(CH3OH)2]·py (sal = salicylate, py = pyridine) 1 and (HNEt3)2[Mn(sal)3] 2 have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction analyses. Crystal data for compound 1: monoclinic, space group C2/c, a = 30.748(6), b = 8.1933(13), c = 21.137(4) °, β = 126.772(4)°, V = 4265.5(13) 3, Z = 8, Mr = 471.34, Dc = 1.468 g/cm3, μ = 0.667 mm-1, F(000) = 1952, the final R = 0.0637, wR = 0.1783 (I > 2σ(I)) and GOOF = 1.073; and those for compound 2: monoclinic, space group C2/c, a = 14.505(5), b = 11.048(4), c = 20.711(7) , β = 103.603(6)°, V = 3225.6 (18) 3, Z = 4, Mr = 668.65, Dc = 1.377 g/cm3, μ = 0.466 mm-1, F(000) = 1416, the final R = 0.0373, wR = 0.1125 (I > 2σ(I)), and GOOF = 1.000. The Mn atoms of both complexes are six-coordinated in an axially elongated octahedral geometry for 1 and an axially compressed octahedral geometry for 2, and their oxidation states have been determined to be trivalent by bond valence sum calculation.     

类蝎型铜配合物的合成、结构及光谱特征

在四氢呋喃体系中合成了一个具有平面结构的三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(简称bpz*eaT), 并以其为配体, 在无水乙醇溶剂中合成了2个新配合物₂·(CuCl₄)(1)和Cu_1.5Cl₃(bpz*eaT)(2). 通过元素分析、红外光谱、紫外光谱、荧光光谱、热重分析、X射线粉末衍射以及X射线单晶衍射等方法对配合物进行了表征, 分析了其光谱及结构特征. 结构分析表明, bpz*eaT采取三齿螯合配位模式, 配合物1和2中的铜均为五配位, 形成了扭曲的四角锥构型. 采用密度泛函理论(DFT)中的B3LYP方法研究了这2个配合物的稳定性和电荷分布.     

Syntheses and Structures of Three Novel 1-D Lanthanide-isonicotinate Coordination Polymers

1 INTRODUCTION In the past decade or so far, the construction of extended multidimensional coordination polymers comprised of metal ions as nodes and bridged ligand as linkers or spacers of self-assembly has attracted considerable attention in supramolecular and materi- als chemistry due to the formation of the intriguing topological structures and potential applications as functional materials[1～4]. In construction of these ex- tended structures, selection of the polydentate orga- nic li…     

Syntheses,Crystal Structures and Bioactivities of Two Novel Isatin Derivatives

Two novel compounds 1-(4-fluorobenzyl)-4-chloro-(Z)-3-benzoylhydrazono-2-indolinone(1) and 1-(4-methoxybenzyl)-(Z)-3-benzoylhydrazono-2-indolinone(2) were synthesized and their crystal structures were determined by single-crystal X-ray diffraction.Compound 1(C22H15ClFN3O2) crystallized in the triclinic system,space group P1·with a=0.94198(19) nm,b=1.4339(3) nm,c=1.5018(3) nm,α=101.58(3)°,β=102.96(3)°,γ=102.73°,V=1.8602(6) nm3,Mr=407.82,Dc=1.456 g/cm3,μ=0.240 mm-1,F(000)=840,Z=4,R1=0.0442 and wR2=0.1064.Comp...