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.     

Selective recognition of H2PO4- by a cholestane-imidazole-zinc ensemble

A new facile amphiphile cholestane-based zinc complex 4 containing a 3-aminopropylimidazole moiety at the 3α and 7α positions of cholestane was designed and synthesized. Recognition selectivity of the new receptor 4 with various anions was assessed by ¹H NMR titration. Dihydrogen phosphate showed the highest binding affinity among all the tested anions (K_a = 4.4 × 10⁵ M^?1).     

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.     

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.     

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.     

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.     

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.     

New mercury vanadium phosphate hydrate Hg(4)(-)(x)()O(1-)(y)()((VO)(PO(4))(2).H(2)O with unprecedented tetrahedral oxo-cluster [Hg( approximately )(4)O( approximately )(5)

The new mercury vanadium phosphate hydrate Hg(4)(-)(x)()O(1)(-)(y)()(VO)(PO(4))(2).H(2)O has been synthesized under hydrothermal conditions. X-ray investigations led to orthorhombic symmetry, space group P2(1)2(1)2(1) (No. 19), a = 6.3632(2) A, b = 12.4155(5) A, c = 14.2292(6) A, Z = 4. The crystal structure was solved and refined from single-crystal diffractometer data to residuals R[F(2) > 2sigmaF(2)] = 0.039, R(w)(F(2)) = 0.055. The VPO framework consists of infinite one-dimensional [VO(PO(4))(2)]( infinity ) chains with corner-connected VO(6) octahedra and PO(4) tetrahedra. The chains run along the [100] direction and are held together by the unprecedented tetrahedral cationic units [Hg(4)(-)(x)()O(1)(-)(y)()](4+). Presence of Hg-Hg bonding contacts is proved from theoretical calculations.     

Terphenyl-phenanthroline conjugate as a Zn(2+) sensor: H(2)PO(4)(-) induced tuning of emission wavelength

A new terphenyl-based macrocycle 5 incorporating phenanthroline as a fluorophore has been designed, synthesized and examined for its recognition ability toward various cations (Pb(2+), Hg(2+), Ba(2+), Cd(2+), Ag(+), Zn(2+), Cu(2+), Ni(2+), Co(2+), K(+), Mg(2+), Na(+) and Li(+)) by UV-vis, fluorescence and NMR spectroscopy. The receptor 5 showed highly selective 'Off-On' fluorescence signaling behavior for Zn(2+) ions in THF. Interestingly, the addition of H(2)PO(4)(-) ions to the [5-Zn] complex regulates the binding site for additional Zn(2+) ions and hence leads to a blue-shifted emission band.     

Two new open framework cobalt phosphates: NaCo3(OH)(PO4)2.1/4H2O and Na(NH4)Co2(PO4)2.H2O

Two new cobalt phosphates, NaCo₃(OH)(PO₄)₂.1/4H₂O (1) and Na(NH₄)Co₂(PO₄)₂.H₂O (2) have been synthesized hydrothermally and characterized by single crystal X-ray diffraction methods, vibrational (IR and Raman) spectroscopy, thermogravimetric analysis and magnetic measurements. The structure of 1 is a new framework type while 2 is an example of a chiral cobalt phosphate. Both phases contain channels in which the Na⁺, NH₄⁺ cations and H₂O molecules are located.     

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.     

Preparation,Single Crystal Structure Analysis,and Thermal Behaviour of the Acidic Mercury(I) Phosphate (Hg2)2(H2PO4)(PO4)

Yellowish single crystals of acidic mercury(I) phosphate (Hg₂)₂(H₂PO₄)(PO₄) were obtained at 200 °C under hydrothermal conditions in 32% HF from a starting complex of microcrystalline (Hg₂)₂P₂O₇. Refinement of single crystal data converged at a conventional residual R[F² > 2σ(F²)] = 3.8% (C2/c, Z = 8, a = 9.597(2) Å, b = 12.673(2) Å, c = 7.976(1) Å, β = 110.91(1)°, V = 906.2(2) ų, 1426 independent reflections > 2σ out of 4147 reflections, 66 variables). The crystal structure consists of Hg₂²⁺‐dumbbells and discrete phosphate groups H₂PO₄^– and PO₄^3–. The Hg₂²⁺ pairs are built of two crystallographically independent Hg atoms with a distance d(Hg1–Hg2) = 2.5240(6) Å. The oxygen coordination sphere around the mercury atoms is asymmetric with three O atoms for Hg1 and four O atoms for Hg2. The oxygen atoms belong to the different PO₄ tetrahedra, which in case of H₂PO₄‐groups are connected by hydrogen bonding. Upon heating over 230 °C, (Hg₂)₂(H₂PO₄)(PO₄) condenses to (Hg₂)₂P₂O₇, which in turn disproportionates at higher temperatures into Hg₂P₂O₇ and elemental mercury.     

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.     

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.     

Synthesis of the arachno-4-CB(8)H(12)(2)(-) monocarbaborane dianion and NMR/computational studies of the fluxional processes observed in the isoelectronic nine-vertex arachno anions: arachno-4-CB(8)H(12)(2)(-), arachno-4-CB(8)H(13)(-), and arachno-4-SB(8)H(11)(-)

The new monocarbaborane dianion, arachno-4-CB(8)H(12)(2)(-) has been synthesized from the reaction of arachno-4-CB(8)H(14) with 2 equiv of NaH in polar solvents. DFT/GIAO computations at the B3LYP/6-311G//B3LYP/6-311G level, in conjunction with 1D and 2D NMR spectroscopic studies, have confirmed that the dianion results from deprotonation of both the endo-CH and one bridging hydrogen of the parent arachno-4-CB(8)H(14). While the DFT calculations indicate that a C(1) symmetric structure is lowest in energy, the experimental solution NMR data are consistent with the dianion having a C(s)() symmetric structure, thus suggesting that it is fluxional in solution. Transition state calculations located a low-energy pathway with an activation energy of only 2.7 kcal/mol that allows the migration of the bridging hydrogen between the two enantiomeric forms of the dianion. The process can occur by a single-step, simple rotation through a transition state structure containing a -BH(2) group at the B7 boron. Averaging the calculated (11)B NMR chemical shifts of the resonances for those atoms in the static enantiomeric structures that become equivalent by this fluxional process then gives excellent agreement with the solution NMR data. Transition state calculations of the fluxional behavior previously observed for the isoelectronic arachno-4-CB(8)H(13)(-) and arachno-4-SB(8)H(11)(-) monoanions have likewise revealed related low-energy (0.3 and 5.0 kcal/mol, respectively) rearrangement mechanisms involving the simultaneous rotation of three hydrogens (two bridging and one -BH(2)) through a C(s)() symmetry transition state containing three -BH(2) groups.