一种新型的一维杂化磷酸锌化合物(2,2′-bipy)2·Zn2(PO4H)(PO4H2)2的合成与结构表征

作为磷酸盐基空旷骨架(Open-framework)化合物的一个重要组成部分, 磷酸锌基空旷骨架化合物经过近10年的发展已经成为内涵丰富的一个族系[1～6]. 实验证明有机胺基团可以作为配体, 起到电荷平衡阳离子与磷酸锌构成骨架作用[1～6]. 我们认为, 有机胺和骨架上的部分锌原子键合方式与多金属氧酸盐中的配体-次级金属结构模型存在相似性. 因此, 将多金属氧酸盐的配体-次级金属模型向过渡金属磷酸盐领域进行"嫁接", 不仅存在着实验参考依据[3,4], 而且将会推动磷酸盐配位化学的发展. 与多面体构成的钼酸盐和钒酸盐相比较, 这种"嫁接"意味着以磷氧四面体为结构单元的过渡金属磷酸盐可能存在着新颖的拓扑结构. 我们选用2,2′-联吡啶作为螯合配体, 制备新颖的具有杂化磷酸锌骨架的化合物, 并通过刚性配体的空间效应在一定程度上限制磷酸锌聚合体的外延连接. 本文报道一种一维链状杂化磷酸盐(2,2′-bipy)2Zn2(PO4H)(PO4H2)2(以下简称FJ-10, FJ: Fujian Institute of Research on the Structure of Matter)的水热合成及单晶结构表征. 在磷酸锌体系中, FJ-10具有新颖的骨架拓扑结构和堆垛方式. 我们将对此类化合物的合成、结构与性质进行系列报道.     

Highly effective fluorescent sensor for H2PO4(-)

A new anthracene dimer connected by two imidazolium moieties has been systematically designed and synthesized as a fluorescent chemosensor for selective binding of H(2)PO(4)(-) over other anions, which have been examined using fluorescence and (1)H NMR and rationalized with ab initio study.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Synthesis and characterization of a new three-dimensional lanthanide carboxyphosphonate: Ln(4)(H(2)O)(7)[O(2)C-C(5)H(10)N-CH(2)(-)PO(3)](4)(H(2)O)(5)

The first open-framework lanthanide carboxyphosphonate has been obtained under hydrothermal conditions. The three-dimensional structure of MIL-84(Pr) (MIL = Material Institut Lavoisier) or Pr(4)(H(2)O)(7)[O(2)C-C(5)H(10)N-CH(2)(-)PO(3)](4)(H(2)O)(5) has been solved from X-ray diffraction single-crystal data (a = 23.481(1) A, b = 10.159(1) A, c = 23.006(1) A, beta = 105.63(1) degrees, V = 5284.6(6) A(3), space group Cc (No. 9)). Its framework is built up from chains of edged-sharing eight or nine-coordinated monocapped square antiprism polyhedra and carboxyphosphonate anions, creating a three-dimensional structure with small pores filled with water molecules. The thermal behavior of MIL-84(Pr) has been investigated using TGA and X-ray thermodiffractometry and indicates that MIL-84(Pr) is stable up to 523 K with a reversible hydration-dehydration process. The optical study of its yttrium analogue doped at 3.4% with europium (MIL-84(Y,Eu)) reveals a significant red-orange emission under UV radiation.     

Synthesis and Structure of a Molecular Zinc Phosphate [(C12H8N2Zn)2(HPO4)(H2PO4)2]

A hydrothermal reaction of a mixture of ZnCO₃, phosphoric acid, 1, 10‐phenanthroline in H₂O gave rise to large plates of a new zinc phosphate, [(C₁₂H₈N₂Zn)₂(HPO₄)(H₂PO₄)₂], I . The structure consists of ZnO₃N₂ distorted trigonal‐bipyramidal and PO₄ tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)ų, Z = 8.     

Muon spin relaxation study of Zr(H2PO4)(PO4).2H2O

Muon spin relaxation has been used to study the muon dynamics in the layered zirconium phosphate Zr(H(2)PO(4))(PO(4)).2H(2)O as a function of temperature. Radiofrequency decoupling was used to establish the origin of the local dipolar field as coupling with (1)H spins. Muons were trapped at two sites, one identified as HMuO and the other consistent with PO-Mu on the basis of their zero-field second moments. Although a small decrease in the local nuclear dipolar field was seen with temperature, the muons remained essentially static over the temperature range 20-300 K.     

A simple and efficient colorimetric anion receptor for H(2)PO(4)(-)

A novel and neutral anion sensor bearing a urea group as binding sites and 2,4-di nitrophenylhydrazine unit as a molecular architecture and a chromophore was synthesized and the visible color changes, the UV-vis and (1)H NMR spectral responses toward anions were assessed.     

(NH 4 )Zn 2 (PO 4 )(HPO 4 ): Hydrothermal Synthesis and Reaction with n-Alkylamine Vapours

(NH₄)Zn₂(PO₄)(HPO₄) was synthesized under mild hydrothermal conditions in the presence of urea. The reaction with n-alkylamines has been investigated by exposing the solid to amines vapor. The new materials were characterized by chemical and thermal analysis, powder X-ray diffraction, and IR spectroscopy. In addition, the simultaneous reaction of this compound with two or more n-alkylamine different molecules was investigated. The reaction of large n-alkylamine molecules was observed to be faster if there is a shorter alkyl chain amine acting as a catalyst, yielding on completion single amine materials. In the case of a vapor mixture of several amines, the compound obtained depends on the reaction time.     

Two organically templated niobium and zinconiobium fluorophosphates: low temperature hydrothermal syntheses of NbOF(PO4)2(C2H10N2)2 and Zn3(NbOF)(PO4)4(C2H10N2)2

Two new niobium and zinconiobium fluorophosphates, NbOF(PO4)2(C2H10N2)2 (1) and Zn3(NbOF)(PO4)4-(C2H10N2)2 (2), have been prepared under hydrothermal conditions using ethylenediamine as a template. The structures were determined by single crystal diffraction to be triclinic, space group P1 (No. 2), a = 8.1075 (6) A, b = 9.8961 (7) A, c = 10.1420(8) A, alpha = 111.655(1) degrees, beta = 111.51(1) degrees, gamma = 93.206(1) degrees, V = 686.19(9) A3, and Z = 2 for 1 and orthorhombic, space group Fddd (No. 70), a = 9.1928(2) A, b = 14.2090(10) A, c = 32.2971 (6) A, V = 4218.66(12) A3, and Z = 8 for 2, respectively. Compound 1 is an infinite linear chain consisting of corner-sharing [Nb2P2] 4-MRs bridged at the Nb centers with organic amines situated between chains, and compound 2, containing the chains similar to that in 1, forms a zeotype framework with organic amines situated in the gismondine-type [4684] cavities. The topology of 2 was previously unknown with vertex symbol 4 x 4 x 4 x 4 x 8 x 8 (vertex 1), 4 x 4 x 4 x 82 x 8 x 8 (vertex 2), 4 x 4 x 8 x 8 x 82 x 82 (vertex 3), and 4 x 4 x 4 x 82 x 8 x 8 (vertex 4). The topological relationships between the 4-connected network of 2 and several reported (3,4)-connected networks were discussed.     

Small gas-phase dianions of Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-)

We have searched for new species of small oxygen-containing gas-phase dianions produced in a secondary ion mass spectrometer by Cs+ ion bombardment of solid samples with simultaneous exposure of their surfaces to O2 gas. The targets were a pure zinc metal foil, a copper-contaminated zinc-based coin, two silicon-germanium samples (Si(1-x)Ge(x)(with x= 6.5% or 27%)) and a piece of titanium metal. The novel dianions Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-) have been observed at half-integer m/z values in the negative ion mass spectra. The heptamer dianions Zn3O(4)(2-) and Ti2O(5)(2-) have been unambiguously identified by their isotopic abundances. Their flight times through the mass spectrometer are approximately 20 micros and approximately 17 micros, respectively. The geometrical structures of the two heptamer dianions Ti2O(5)(2-), and Zn3O(4)(2-) are investigated using ab initio methods, and the identified isomers are compared to those of the novel Ge2O(5)(2-) and the known Si2O(5)(2-) and Be3O(4)(2-) dianions.     

Cu4(CH3C(OH)(PO3)2)2(C4H4N2)(H2O)4: a novel,three-dimensional copper diphosphonate with metamagnetism

A novel, three-dimensional copper diphosphonate Cu4(CH3C(OH)(PO3)2)2(C4H4N2)(H2O)4 (1) incorporating an organic pyrazine ligand has been hydrothermally synthesized, which exhibits antiferromagnetic ordering below 4.2 K and metamagnetic behavior.     

The Pd(4)(dppm)(4)(H)(2)(2+) cluster: a precatalyst for the homogeneous hydrogenation of alkynes

The catalytic properties of the title cluster toward the homogeneous hydrogenation of phenylacetylene, diphenylethyne and phenyl-1-propyne have been investigated as a function of temperature, pressure, solvents, substrate and cluster concentrations, and counterions. The title cluster is a precatalyst that exhibits a good catalytic activity under mild conditions (1 atm of H(2) at 20 degrees C) for the hydrogenation of alkynes and alkenes. For the alkyne substrates, the turnover frequencies (tof's) range between 200 and 500 h(-)(1), and the product distribution varies as: cis-products, 75-90%; trans-products; 0-8% after 3 h of reaction. Based on the graphs -d[substrate]/dt vs [Pd(4)](1/2), the mechanism indicates a cluster dissociation into two dimers (presumably of the type Pd(2)(dppm)(2)(H)(solvent)(+)). The variations of tof (or -d[substrate]/dt) as a function of [substrate] and pressure of H(2) are linear. At 1600 psi of H(2), the tof can reach 2500-3000 h(-)(1) (in THF). The tof also increases with temperature reaching a maximum at approximately 35 degrees C (tof: 1000-1300 h(-)(1)), but at higher temperatures cluster decomposition begins to occur, leading to a rapid decrease in rates of catalysis. At 50 degrees C, no catalysis is observed. The hydrogenation reaction can be stopped at the corresponding cis-alkenes with approximately 95% yields, depending on the substrate and experimental conditions used. The tof's also vary with the solvent, where stronger coordinating solvent molecules give higher tof's. In addition, the tof's do not change with the nature of the counterion, which acts as "spectator" in the catalysis.     

Synthesis and characterisation of (C4N2H12)(UO2)2(PO3H)2(PO2(OH)H)2: a three dimensionally connected actinide framework

The material (C4N2H12)(UO2)2(PO3H)2(PO2(OH)H)2 (MUPH-1) has been prepared hydrothermally; it is a three dimensional structure consisting of four intersecting elliptical shaped one-dimensional channels, the largest channel has dimensions of 13.1 x 7.2 A.     

Doppelkettenstruktur von (pipzH2)[MnF2(HPO4)(H2O)](H2PO4)

By adding piperazine to a hydrofluoric and phosphoric acid solution of Manganese(III) fluoride, the fluoride phosphate (pipzH₂)[MnF₂(HPO₄)(H₂O)](H₂PO₄) can be crystallized. Its structure is built by piperazinium(2+) cations, (H₂PO₄)^? anions, and an anionic double‐chain of [HPO₄] tetrahedra and [MnO₃F₂(H₂O)] octahedra. The structure is triclinic, space group P , Z = 2, a = 622.97(4), b = 923.46(6), c = 1183.62(7) pm, α = 98.343(6)°, β = 100.747(7)°, γ = 107.642(5)°, R = 0.0289. It is worth noting that a ferrodistortive Jahn‐Teller order is observed with [MnO₃F₂(H₂O)] octahedra strongly elongated along the F–Mn–OH₂ axes perpendicular to the chain plane. The structure is stabilized by very strong hydrogen bonds.     

Zn6[MeN(CH2CO2)(CH2PO3)](6)(Zn)]4- anion: the first example of the oxo-bridged Zn6 octahedron with a centered Zn(II) cation

Hydrothermal reactions of N-(phosphonomethyl)-N-methylglycine, MeN(CH(2)CO(2)H)(CH(2)PO(3)H(2)) (H(3)L), with zinc(II) acetate resulted in the formation of a novel zinc carboxylate-phosphonate, [Zn(6)L(6)(Zn)][Zn(H(2)O)(6)](2) x 22H(2)O (1). The structure of 1 contains a heptanuclear zinc phosphonate cluster anion, [Zn(6)L(6)(Zn)](4-), in which seven zinc(II) cations form an unusual Zn(6)(Zn) centered octahedron with six of its Zn(3) triangle faces each further capped by a phosphonate group. The Zn(II) cations of the Zn(6) octahedron are five-coordinated whereas the centered Zn(II) cation is octahedrally coordinated. Packing of these cluster anions creates micropores occupied by the hydrated zinc(II) cations as well as lattice water molecules. The structural skeleton of 1 is retained after the removal of the lattice water molecules.     

Polymorphism of [Zn(2,2′‐bipy)(H2PO4)2]2

Two polymorphs of a zero‐dimensional (molecular) zinc phosphate with the formula [Zn(2,2′‐bipy)(H₂PO₄)₂]₂ have been synthesized by a mild hydrothermal route and their crystal structures were determined by single crystal X‐ray diffraction (triclinic, space group (No. 2), Z = 2, α‐form: a = 8.664(1), b = 8.849(2), c = 10.113(2) Å, α = 97.37(2)°, β = 100.54(2)°, γ = 100.98(2)°, V = 737.5(3) ų; β‐form: a = 7.5446(15), b = 10.450(2), c = 10.750(2) Å, α = 67.32(3)°, β = 81.67(3)°, γ = 69.29(3)°, V = 731.4(3) ų). Both structures consist of distorted trigonal‐bipyramidal ZnO₃N₂ units condensed with PO₂(OH)₂ tetrahedra through common vertices giving rise to dimers [Zn(2,2′‐bipy)(H₂PO₄)₂]₂. The structures are stabilized by extensive inter‐ and intramolecular hydrogen bond interactions. Both modifications display subtle differences in their packing originating from the hydrogen bond interactions as well as π…π interactions between the organic ligands.     

Synthesis and characterization of (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, a layered gallium phosphatooxalate containing a chiral amine

The first metal phosphatooxalate containing a chiral amine, (R-C5H14N2)2[Ga4(C2O4)(H2PO4)2(PO4)4].2H2O, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction and 31P MAS NMR spectroscopy. It crystallizes in the monoclinic space group P2(1) (No. 4) with a = 8.0248(4) A, b = 25.955(1) A, c = 9.0127(5) A, beta = 100.151(1) degrees, and Z = 2. The structure consists of GaO6 octahedra and GaO4 tetrahedra connected by coordinating C2O4(2-) and phosphate anions to form anionic sheets in the ac plane with charge-compensating diprotonated R-2-methylpiperazinium cations and water molecules between the layers. There is a good correlation between the NMR spectrum and the structure.     

Fluorescent acridine-based receptors for H2PO4(-)

Two new pseudopeptidic molecules (one macrocyclic and one open chain) containing an acridine unit have been prepared. The fluorescence response of these receptors to a series of acids was measured in CHCl(3). Receptors are selective to H(2)PO(4)(-) versus HSO(4)(-), and an even higher selectivity is found over other anions such as Cl(-), Br(-), CH(3)COO(-), and CF(3)COO(-). We show that the macrocyclic receptor is more selective for H(2)PO(4)(-) than the related open chain receptor. The supramolecular interactions of triprotonated receptors with different anions have been modeled in silico and have been studied by different experimental techniques. Optimized geometries obtained by computational calculations agree well with experimental data, in particular fluorescence experiments, suggesting that the selective supramolecular interaction takes places through coordination of the anions to the triprotonated form of the receptor.     

A Zn(2+) specific triazole based calix[4]arene conjugate (L) as a fluorescence sensor for histidine and cysteine in HEPES buffer milieu

A highly fluorescent Zn(2+) complex of the triazole linked salicyl-imino-thiophenyl conjugate of calix[4]arene, [ZnL] has been demonstrated to be a chemo-sensing ensemble for the recognition of His and Cys among the naturally occurring amino acids in HEPES buffer milieu. The recognition behaviour of the [ZnL] towards these amino acids has been shown on the basis of fluorescence, absorption and visual fluorescent colour changes. The species of recognition were shown by ESI MS titrations, AFM & TEM microscopy and cell studies.