新型层状氟化磷酸铝[C4H12N2][Al2(PO4)2(H2O)2F2]的水热合成与表征

自从1982年Wilson等发现一类新型微孔材料磷酸铝分子筛(AlPO4-n)以来,大量具有新颖结构的磷酸铝化合物被合成出来,它们在催化、离子交换、吸附和主-客体组装等方面均具有潜在的应用前景,这类化合物大多是在水热或溶剂热体系中和有机模板剂存在条件下合成的,1978年,Flanigen等首先在反应体系中加入氟离子作矿化剂合成了硅晶体,后来,氟离子方法在硅铝体系和金属磷酸盐体系中也得到了广泛的应用,氟离子在反应过程中起到矿化剂或结构导向剂的作用,     

用分子动力学模拟方法研究层孔与微孔磷酸铝化合 物中有机胺的模板作用: 指 导定向合成的有效途径

用分子动力学方法,研究了有机胺模板剂对二维层孔与三维微孔磷酸铝化合物的模板作用。依据主-客体间的非键相互作用能量,可以有效地预测出适于某一特定结构的有机胺模板剂。通过选择理论预测的有机胺分子作模板剂,在溶剂热体系中可以定向地合成出具有特定结构的化合物。这一工作对于微孔功能体系的分子工程学研究具有一定的指导意义。     

用分子动力学模拟方法研究层孔与微孔磷酸铝化合 物中有机胺的模板作用: 指 导定向合成的有效途径

用分子动力学方法,研究了有机胺模板剂对二维层孔与三维微孔磷酸铝化合物的模板作用。依据主-客体间的非键相互作用能量,可以有效地预测出适于某一特定结构的有机胺模板剂。通过选择理论预测的有机胺分子作模板剂,在溶剂热体系中可以定向地合成出具有特定结构的化合物。这一工作对于微孔功能体系的分子工程学研究具有一定的指导意义。     

模板固相合成磷酸铝及其表征

Ｔ－磷酸铝的合成用水热方法,需９５０℃,２０天才能得到［１］。研究结果表明用固相方法,１５０℃,２小时合成了Ｔ－磷酸铝,同样条件下有模板存在可以得到磷酸铝微晶和Ｔ－磷酸铝,用ＸＲＤ、ＩＲ、ＩＣＰ和化学分析方法对产物进行了表征。 磷酸铝是一类具有广而重要应用的材料,过去十多年里,应用模板在胶态介质中水热方法合成了具有微孔、小孔、中孔的一系列磷酸铝类材料。由于其具有多种结构和组成,对热和水热的稳定性,使得它们在吸附分离、催化剂及催化剂载体、土壤科学、污水处理、医药上调节胃酸等中起着重要作用。特别是在…     

一种新型杂化单晶[Ga3(PO4)3F2]H3O·(H3NCH2CH2)2NH2的合成与结构表征

自从系列磷酸铝微孔晶体首次被报道以来, 空旷骨架磷酸盐化合物的合成取得了长足进展[1,2]. 其中, 空旷磷酸镓骨架化合物以其丰富的拓扑连接方式成为研究的热点之一[1,3,4]. 特别是向水热合成体系中引入氟离子, 导致了新颖微孔磷酸镓化合物的不断出现, 如磷酸镓-CLO[5], 磷酸镓MIL-31[6]等化合物. 目前, 合成实验表明, 乙烯胺类化合物(如二乙烯三胺)因其构象变化复杂, 可以诱导出多种新颖空旷骨架磷酸盐[7～9]. 由于氟离子可以同磷酸镓骨架中的镓原子配位, 进而改变骨架拓扑连接方式和电荷分布, 因此氟原子与二乙烯三胺协同作用可能获得新颖的无机骨架与导向剂的自组装模型.     

磷酸铝分子筛AlPO_4-5的常压快速合成及晶化过程的原位热重-质谱研究

分别以三乙胺、环己胺和四乙基氢氧化铵为结构导向剂,二缩三乙二醇为溶剂,研究了3种溶剂热合成体系在常压和自生压力条件下的晶化行为.在常压加热条件下,从分别含有三乙胺、环己胺和四乙基氢氧化铵的初始凝胶中快速晶化出了高结晶度的磷酸铝分子筛AlPO_4-5.在自生压力加热条件下,从相同的初始凝胶中分别晶化出了三维开放骨架磷酸铝JDF-20、二维层状磷酸铝UT-5以及含有磷酸铝分子筛AlPO_4-5的混相.含有三乙胺的初始凝胶晶化过程的原位热重-质谱研究表明,常压条件下磷酸铝分子筛AlPO_4-5主要在150~300℃之间生成.实验表明,自生压力会对有机胺(铵)的结构导向效应产生显著影响,这加深了对分子筛以及开放骨架生成过程及机理的认识.     

新型三维开放骨架磷酸铝化合物的合成及晶化过程中的共模板效应

以1,2-丙二胺(1,2-DAP)为结构导向剂,在180℃加热摩尔组成为n(Al_2O_3)∶n(P_2O_5)∶n(1,2-DAP)∶n(H_2O)=1∶6∶5.5∶139的初始混合物,合成了具有AlPO-CJ31骨架结构的新型三维开放骨架磷酸铝化合物(1);加热摩尔组成为n(Al_2O_3)∶n(P_2O_5)∶n(1,2-DAP)∶n(H_2O)=1∶6∶7.5∶139的初始混合物,合成了二维层状磷酸铝化合物APDAP_(12)-150.利用X射线粉末衍射分析(XRD)、元素分析、热重/差热分析等表征手段确认了化合物1的分子式为[Al_4P_5O_(20)·H_3O·H_2O]·[H_3NCH_2CHNH_3CH_3],质子化的水分子与双质子化的1,2-丙二胺共同起到了导向化合物1的作用.调变初始混合物中1,2-丙二胺的比例可显著影响其模板效应.1,2-丙二胺比例较低[n(1,2-DAP)=5.5]时,产物为三维开放骨架化合物,而当其比例较高[n(1,2-DAP)=7.5]时,产物为二维层状化合物.     

具有AWO分子筛结构的磷酸铝[Cu(en)2]0.5[Al3P3O12(OH)]:合成、结构与相转变

利用水热合成方法,以自组装的铜胺配合物为模板剂,合成出具有AWO分子筛结构的磷酸铝微孔化合物[Cu(en)2]0.5[Al3P3O12(OH)],命名为AlPO-CJ53.单晶结构解析表明,其结晶在单斜晶系/P21/n(No.14)空间群,晶胞参数为:a=0.85547(11)nm,b=1.7671(2)nn,c=0....     

芳香胺对微孔层状磷酸铝材料的剥离与嵌入

用XRD和SEM研究了芳香胺对微孔层状磷酸铝 [Al3P4O16][CH3CH2NH3]3和[Al2P3O10(OH)2]•[C6NH8]的剥离和嵌入过程, 结果发现, 芳香胺本身的碱性大小是形成新的柱撑物的关键. 卞胺是碱性较强的芳香胺, 可以很好地将磷酸铝剥离并嵌入到层间形成新的层状化合物; 而碱性较弱的苯胺却无法做到. 新柱撑物形成的速度除与介质的介电常数和芳香胺的加入量有关外, 还取决于原有磷酸铝层板间相互作用的强弱.     

基于数据挖掘方法的开放骨架磷酸铝定向合成参数分析

开放骨架磷酸铝化合物是多孔晶体材料的一个重要家族。然而,这类材料的合成受到反应原料、凝胶组成、溶剂、模板剂、结晶温度和结晶时间等多个因素的影响。本文以吉林大学“无机制备与合成化学国家重点实验室”建立的开放骨架磷酸铝合成反应数据库为研究对象,采用最大权重最小冗余特征选择算法(Maximum weight and minimum redundancy,MWMR),在充分考虑合成参数自身的重要程度和合成参数之间的相关关系的前提下,分析了溶剂、模板剂等合成参数对于合成含有(8,6)元环结构开放骨架磷酸铝的影响。通过大量实验验证了该方法在开放骨架磷酸铝合成参数分析中的有效性,分析了合成参数对产物生成的影响。实验结果表明模板剂的几何参数、模板剂中C原子和N原子的个数比,溶剂的偶极距等参数可能对于该类结构的合成具有较为重要的影响。     

A pentanuclear bimetallic complex of manganese(II) and aluminium(III) ions: tetra‐μ2‐iodido‐iodidobis(μ3‐2‐methoxyethanolato)bis(μ2‐2‐methoxyethanolato)dimethyl(tetrahydrofuran‐κO)aluminium(III)tetramanganese(II)

The molecule of the title compound, [Mn₄Al(CH₃)₂(C₃H₇O₂)₄I₅(C₄H₈O)], contains one Al^III and four Mn^II ions. Two Mn atoms are five‐coordinate in the form of a trigonal bipyramid or a square pyramid. The two other Mn atoms are six‐coordinate with an octahedral geometry. The fourcoordinate Al atom is linked to the manganese core by μ‐O_alkoxo bridges, forming an almost planar five‐membered ring.     

The solid solution (Fe0.81Al0.19)(H2PO4)3 with a strong hydrogen bond

Single crystals of the solid solution iron aluminium tris(dihydrogenphosphate), (Fe_0.81Al_0.19)(H₂PO₄)₃, have been prepared under hydrothermal conditions. The compound is a new monoclinic variety (γ‐form) of iron aluminium phosphate (Fe,Al)(H₂PO₄)₃. The structure is based on a two‐dimensional framework of distorted corner‐sharing MO₆ (M = Fe, Al) polyhedra sharing corners with PO₄ tetrahedra. Strong hydrogen bonds between the OH groups of the H₂PO₄ tetrahedra and the O atoms help to consolidate the crystal structure.     

Novel K/Mn phosphate hydrates,K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K₂Mn₃(H₂O)₂[P₂O₇]₂, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H₂O)₂[Al₂(PO₄)₃], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X‐ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A₂M₃(H₂O)₂[P₂O₇]₂, where A = K, NH₄, Rb or Na and M = Mn, Fe, Co or Ni, and AM²⁺(H₂O)₂[M³⁺₂(PO₄)₃], where A = Cs, Rb, K, NH₄ or (H₃O); M²⁺ = Mn, Fe, Co or Ni; and M³⁺ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit‐cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO₂)₂(PO₄)₂]_∞ layers, with a cationic topology similar to the Si/Al‐topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.     

Two distinct manganese molybdenum(V) phosphates directed by different organic amines

By employing different organic amines as structure-directing agents, two new distinct 3D porous inorganic frameworks based on molybdenum(V) phosphates and Mn^II, (H₂en)₂{[Mn(H₂O)]₂[MnMo₁₂O₂₄(OH)₆(H₂PO₄)₂(HPO₄)₄(PO₄)₂]}·7H₂O (en = ethylenediamine) (1) and (H₃dien)₂{[Mn(H₃O)₂][Mn₃Mo₁₂O₂₄(OH)₆(HPO₄)₂(PO₄)₆]}·5H₂O (dien = diethylenetriamine) (2), have been hydrothermally synthesized, and characterized by routine physical methods. In compound 1, Mn^II all adopt octahedral coordination mode and each sandwich cluster Mn[Mo₆P₄O₃₁]₂ (abbreviated as Mn[Mo₆P₄]₂) acts as an octa-dentate ligand linking eight Mn^II, which result in a 3D inorganic (4, 8)-connected framework with the (4⁶)(4¹⁰·6¹²·8⁶) topology. Compound 2 shows a 3D (4, 10)-connected framework with the (3¹·4⁴·6¹)(3⁴·4⁹·5⁷·6¹⁷·7⁴·8⁴) topology, in which Mn^II ions exhibit both tetrahedral and octahedral coordination modes, and each Mn[Mo₆P₄]₂ links ten Mn^II. Interestingly, there exist channels along the a and b axes in 1, while along the a and c axes in 2. The differences between the two compounds should be ascribed to the distinctions of the organic amines. Primary de-/rehydration behaviors and electrochemistry properties have also been studied for the two compounds.     

Crystal Structure of Calcium-Deficient Carbonated Hydroxyapatite. Thermal Decomposition

Full Rietveld refinement of the crystal structure of the synthetic calcium-deficient carbonated apatite Ca1_3.40[Ca2_5.90 (NH₄)_0.10][(PO₄)_4.95(CO₃)_1.05(H₂O)_0.30][(OH)_1.65(H₂O)_0.45] (space group P6₃/m; a=9.437(1), c=6.888(1) Å; Z=1; R_wp=5.23%) was carried out using X-ray powder diffraction data. The use of the model with the split position of O3 atom made it possible to find two orientations of CO₃ triangles sharing one of their edges. They occupy randomly the adjacent faces of a PO₄ tetrahedron that are parallel to the c axis. O3c atoms coordinating carbon atoms are shifted by 0.37 Å from O3p atoms belonging to PO₄ tetrahedra. The charge unbalance occurring when [CO₃]²⁻ ions replace [PO₄]³⁻ groups is primarily compensated by vacancies in Ca1 sites. The studies of the sample thermal decomposition performed by simultaneous thermal analysis and by X-ray diffraction helped to analyze the localization and the amount of lattice water that enhanced the reliability of the structural model.     

Synthesis,characterization, and magnetochemical properties of two Mn4 clusters derived from 2-pyridinecarboxaldehyde Schiff base ligands

Two tetranuclear manganese complexes, [Mn₄(L¹)₆](ClO₄)₂?2.75H₂O (1) [HL¹ = 4-methyl-2-((pyridin-2-ylmethylene)amino)phenol] and [Mn₄(L²)₄(NO₃)₃(OH)]?pz?3H₂O (2) [HL² = (1H-pyrazol-1-yl)(pyridin-2-yl)methanol, pz = pyrazole], have been synthesized and characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, and magnetic measurements. The structural analysis revealed that the central manganese ion is linked with three apical manganese ions through six phenoxo-bridges creating a Mn₄O₆ core for 1; 2 has a cubane-like topology with the Mn(II) ions and the deprotonated oxygens from L² alternatively occupying vertices. The magnetic studies indicated a weak ferromagnetic coupling interaction (J = 0.48 ± 0.087 cm^?1, g = 2.00, θ = ?0.78 K) for 1 and a weak antiferromagnetic spin-exchange interaction (J₁ = ?0.50 ± 0.075 cm^?1, J₂ = ?0.13 ± 0.082 cm^?1, g = 1.98) between Mn(II) ions for 2. The magnetostructural correlations of the two Mn₄ clusters have been discussed tentatively.     

Two new clusters with MnII-MnIV magnetic exchange from the use of polyalcohol ligands

Two mixed-valence Mn(II,IV) complexes, [Mn^II₄Mn^IV₃(teaH)₃(tea)(thmeH)₃(thme)](ClO₄)₂·3MeCN (1) and [Mn^II₂Mn^IV₂(edteH)₂(peolH)₂]·4MeOH (2), where H₄edte = N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, teaH₃ = tris(2-hydroxyethyl)amine, H₄peol = pentaerythritol, and H₃thme = 1,1,1-tris(hydroxymethyl)ethane, were prepared from the corresponding manganese salts and mixed ligands with polyalcohols. The two clusters consist of a trapped-valence polynuclear core comprising 4Mn^II and 3Mn^IV for 1, 2Mn^II and 2Mn^IV ions for 2. Complex 1 crystallizes in the rhombohedral space group R3c, while 2 crystallizes in the monoclinic space group P2₁/c. Complex 1 consists of a near-planar Mn₇ unit that comprises a Mn₆ hexagon of alternating Mn^II and Mn^IV ions surrounding a central Mn^II ion. The remaining coordinated sites are occupied by eight different deprotonation degrees of H₃tea or H₃thme. The tetranuclear cluster of 2 consists of a fused defective dicubane Mn₄O₆ core, and the four Mn ions are coordinated by oxygens from edteH^3? and peolH^3? into an unusual butterfly-like [Mn^II₂Mn^IV₂] topology. The two clusters are also characterized by mass spectra and X-ray photoelectron spectroscopy. Direct current magnetization studies reveal ferromagnetic interactions within both Mn clusters.     

Di‐μ‐acetato‐bis­[bis(4‐amino­benzoato)(2,2′‐bipyridyl)­manganese(II)]

In the title compound, [Mn₂(C₇H₆NO₂)₂(C₂H₃O₂)₂(C₁₀H₈N₂)₂], the two Mn^II atoms are each coordinated by one 2,2′‐bi­pyridyl mol­ecule, one 4‐amino­benzoate ion and two acetate ions. The two Mn atoms exhibit different coordination environments: one is coordinated by two N and four O atoms, while the other is coordinated by two N and three O atoms. The two Mn atoms are bridged by two acetate ions in a syn–anti mode, with an Mn⋯Mn distance of 4.081 (1) Å.     

Na10(Na,Mn)7Mn43(PO4)36: a new synthetic fillowite‐type phosphate

Na₁₀(Na,Mn)₇Mn₄₃(PO₄)₃₆ (sodium manganese phosphate) was synthesized hydrothermally at 873 K and 0.35 GPa. The complex crystal structure is almost identical to that of natural fillowite‐type phosphates and can be described as a hexagonal packing of three types of rods parallel to the c axis. The rods are constituted by an alternation of five‐ to seven‐coordinated Mn sites [average Mn—O = 2.243 (3) Å], of six‐ to nine‐coordinated Na sites [average Na—O = 2.590 (3) Å], of PO₄ tetrahedra [average P—O = 1.548 (3) Å] and of cation vacancies.     

Copper(II) manganese(II) orthophosphate,Cu0.5Mn2.5(PO4)2

The title compound, Cu_0.5Mn_2.5(PO₄)₂, is a copper–manganese phosphate solid solution with the graftonite‐type structure, viz. (Mn,Fe,Ca,Mg)₃(PO₄)₂. The structure has three distinct metal cation sites, two of which are occupied by Mn^II and one of which accommodates Cu^II. Incorporation of Cu^II into the structure distorts the coordination geometry of the metal cation site from five‐coordinate square‐pyramidal towards four‐coordinate flattened tetrahedral, and serves to contract the structure principally along the c axis.