Hydrothermal synthesis of three-dimensional open-framework beryllium phosphites with 3,4-connected networks

Two new beryllium phosphites, H₂en·Be₃(HPO₃)₄ (1) and H₂pda·Be₃(HPO₃)₄ (2), have been synthesized under hydrothermal conditions. Single-crystal structural analyses reveal that both compounds have three-dimensional inorganic frameworks constructed from strictly alternating BeO₄ tetrahedra and HPO₃ pseudo pyramids. The structure of compound 1 can be described as a pillared layered structure with 12-ring channels. The structure of compound 2 has an interesting sqp topology if Be₃(HPO₃)₄ clusters are regarded as 5-connected nodes in the network.     

Synthesis and characterization of a new organically templated open-framework beryllium phosphite with 3, 4-connected networks

Employing diethylenetriamine (=dien) as a structure-directing agent, a new open-framework beryllium phosphite H₂dien·Be₃(HPO₃)₄ (1), has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction. The structure of 1 features a (3, 4)-connected framework with 8- and 12-ring channels, which is constructed from strictly alternating BeO₄ tetrahedra and HPO₃²⁻ pseudopyramids. The 3-D framework possesses a pcu topology when the heptameric [Be₃(HPO₃)₄] clusters are regarded as 6-connected secondary building units. Crystal data: 1, monoclinic, C2/c (no. 15), a = 8.7350(3) Å, b = 15.1704(6) Å, c = 13.0851(4) Å, β = 101.223(5)°, V = 1700.79(10) Å³, Z = 4, R₁ = 0.0625, wR₂ = 0.1692.     

Flux synthesis of (3,4)-connected zinc phosphites with different framework topologies

Two three-dimensional open-framework zinc phosphites, H₂aem·Zn₃(HPO₃)₄·0.5H₂O (1) and H₂apm·Zn₃(HPO₃)₄ (2), have been synthesized by a phosphorous acid flux method, where aem=4-(2-aminoethyl)morpholine and apm=4-(3-aminopropyl)morpholine. Compound 1 crystallizes in the monoclinic system, P2₁/c, a=9.5852(7) Å, b=20.3941(8) Å, c=10.5339(8) Å, β=94.125(9)°, V=2053.8(2) Å³, Z=4, R₁=0.0319, wR₂=0.0628. Compound 2 crystallizes in the monoclinic system, P2₁/n, a=8.589(2) Å, b=14.020(3) Å, c=16.606(3) Å, β=97.190(8)°, V=1983.9(7) Å³, Z=4, R₁=0.0692, wR₂=0.1479. Both compounds are based on (3,4)-connected networks with 8- and 12-ring channels, which are constructed from Zn₃(HPO₃)₄ clusters as the same secondary building units. These inorganic clusters are spatially organized by different structure-directing agents into different three-dimensional frameworks.     

Three-dimensional metal-organic framework with (3,4)-connected net, synthesized from an ionic liquid medium

A new 3D metal-organic framework with a (3,4)-connected network topology is synthesized from an ionic liquid medium; its highly symmetrical structure comprises doubly interpenetrating nets with the cubic-C3N4 topology.     

A chiral, 16-ring channel framework and a layered caesium zincoarsenate

Caesium zinc arsenate frameworks with a large, chiral pore and an expansive interlayer region have been synthesised.     

A novel low density metal-organic framework with pcu topology by dendritic ligand

A novel low density two-fold interpenetrated MOF-5 analogue with pcu topology, JUC-100, was designed and prepared successfully. It can be regarded as MOF-5 in which half of the Zn(4)O(CO(2))(6) units are replaced by organic 1,3,5-triphenylbenzene segments. JUC-100 exhibits H(2) uptake ability comparable to interpenetrated MOF-5, but relatively low initial isosteric heat of adsorption.     

PKU-10: a new 3D open-framework germanate with 13-ring channels

PKU-10, a germanate with the formula [(CH(3))(4)N](3)Ge(11)O(19)(OH)(9), is synthesized under hydrothermal conditions, and its structure is determined by single-crystal X-ray diffraction data. PKU-10 possesses 3D intersected 13-ring channels and presents a new 6-connectedness linkage mode of the Ge(7) cluster, T(3)P(2)O, forming a pcu topological network. Each Ge(7) cluster is, in fact, surrounded by eight Ge(7) clusters in a nearly perfect cube because the hydrogen bonds between Ge(7) clusters are also taken into account. The structure-directing agent tetramethylammonium (TMA(+)) ions, locating in the channels, can be partially exchanged by Li(+) with retention of the germanate framework. The germanate framework collapses with decomposition of the TMA(+) ions at temperatures higher than 240 °C.     

New lanthanide hybrid as clustered infinite nanotunnel with 3D Ln-O-Ln framework and (3,4)-connected net

A series of new lanthanide hybrids [Ln3(mu-OH)4 (2,5-pydc)(2,5-Hpydc)3(H2O)4]n (Ln = Gd (1), Dy (2), Er (3), Eu (4), Sm (5), Yb (6), Y (7); 2,5-pydc=pyridine-2,5-dicarboxylate), as clustered lanthanide oxide ring tunnels with helical dodecahedral chains and fully 3D Ln-O-Ln connectivity, has been hydrothermally synthesized and characterized. The inorganic skeleton of the hybrid can be specified by the Schl?fli symbol (6210)2 (64102) as a single 3D (3,4)-connected net. The luminescence properties have been studied, and the results showed that the Dy(III) (2) and Eu(III) (4) complexes exhibited sensitized luminescence in the visible region. Variable-temperature magnetic susceptibility measurements of 1-6 showed that the complexes 1-3 are nearly paramagnets, whereas the depopulation of the Stark levels in complexes 4-6 leads to a continuous decrease in mu(eff) when the sample is cooled from 300 to 2 K.     

A chiral tetragonal magnesium-carboxylate framework with nanotubular channels

Reported here is a rare example of a highly symmetrical chiral Mg-based MOF (CPF-1) with nanotubular channels, built from 4(1) (or 4(3)) helical chains. It exhibits a high gas sorption capacity (ca. 1.29 wt% H(2) at 77 K, 1 atm; 84 cm(3) g(-1) of CO(2) at 273 K, 1 atm).     

A chiral porous 3D metal-organic framework with an unprecedented 4-connected network topology

A novel homochiral 3D metal-organic framework [CdL2(H2O)2][ClO4]2.2DMF.3EtOH.5/3H2O, 1, (L =(R)-6,6-dichloro-2,2-diethoxy-1,1-binaphthyl-4,4-bipyridine) exhibits an unprecedented 4-connected network topology owing to the cis- configuration of the Cd coordination and possesses permanent porosity as demonstrated by TGA, XRPD, and CO2 adsorption isotherm studies.     

A new enantiopure unsaturated dicarboxylate as a 4-connected unit in a flexible homochiral PtS-type framework

Metal cation mediated chiral ligand transformation of (S)-camphanic acid leads to a new enantiopure unsaturated dicarboxylate that links tetrahedral Zn(2+) sites into 3-D homochiral 4-connected PtS-type framework structures, Zn(tced) (1, H(2)tced=1,2,2-trimethyl-3-cyclopentene-1,3-dicarboxylic acid) and Zn(4)(tced)(4)(4,4'-bipy) (2, 4,4'-bipy=4,4'-bipyridine).     

A tetrahedrally coordinated cobalt(II) phosphonate with a three‐dimensional framework containing two‐dimensional channels

The structure of poly[caesium(I) [(μ₄‐ethylenediphosphonato)cobalt(II)]], {Cs[Co(C₂H₅O₆P₂)]}_n, reveals a three‐dimensional polymeric open framework consisting of tetrahedral Co^II atoms coordinated by four different ethylenediphosphonate O atoms and intermolecular O—H...O hydrogen bonds. The largest open window is made of corner‐sharing CoO₄ and PO₃C tetrahedra, giving 16‐membered rings of dimensions 9.677 (5) × 4.684 (4) Ų. There are two independent ethylenediphosphonate ligands, each lying about an inversion centre.     

Analysis of drug interactions with very low density lipoprotein by high-performance affinity chromatography

High-performance affinity chromatography (HPAC) was utilized to examine the binding of very low density lipoprotein (VLDL) with drugs, using R/S-propranolol as a model. These studies indicated that two mechanisms existed for the binding of R- and S-propranolol with VLDL. The first mechanism involved non-saturable partitioning of these drugs with VLDL, which probably occurred with the lipoprotein’s non-polar core. This partitioning was described by overall affinity constants of 1.2 (±0.3)?×?10⁶ M^?1 for R-propranolol and 2.4 (±0.6)?×?10⁶ M^?1 for S-propranolol at pH 7.4 and 37 °C. The second mechanism occurred through saturable binding by these drugs at fixed sites on VLDL, such as represented by apolipoproteins on the surface of the lipoprotein. The association equilibrium constants for this saturable binding at 37 °C were 7.0 (±2.3)?×?10⁴ M^?1 for R-propranolol and 9.6 (±2.2)?×?10⁴ M^?1 for S-propranolol. Comparable results were obtained at 20 and 27 °C for the propranolol enantiomers. This work provided fundamental information on the processes involved in the binding of R- and S-propranolol to VLDL, while also illustrating how HPAC can be used to evaluate relatively complex interactions between agents such as VLDL and drugs or other solutes.     

A (3,9)-connected cadmium 1,2,4-triazolate framework based on a trinuclear inorganic cluster

Hydrothermal reaction of 1,2,4-triazole with CdCl₂?·?2.5H₂O generated a 3-D metal-organic framework, {[Cd₃Cl₂(Trz)₄]?·?H₂O} _n (1) (Trz?=?1,2,4-triazole), which was characterized by elemental analysis, FT-IR, X-ray powder diffraction, X-ray single-crystal diffraction, TG/DTA, and photoluminescence measurements. Compound 1 crystallizes in the orthorhombic system, space group Pnma, a?=?16.906(3)?Å, b?=?8.3151(17)?Å, c?=?13.080(3)?Å, V?=?1838.6(6)?ų, Z?=?4. Cd(1) is coordinated by four nitrogen atoms and one chloride to form a distorted trigonal-bipyramidal geometry. Cd(2) is an octahedron defined by four triazole nitrogen atoms and two chlorides. Two Cd(2) and one Cd(1) are linked by μ ₃-Cl(1) to give a [Cd₃Cl] cluster, which is connected by μ ₂-Cl(2) to generate a 1-D inorganic chain. The 1-D inorganic chains are extended by μ ₃-Trz to form a 2-D hybrid layer in the b, c-plane, which is ultimately linked by residual triazole ligands to give a 3-D framework. The [Cd₃Cl] clusters and the Trz ligands can be regarded as 9- and 3-connected nodes, which lead to an unusual (3,9)-connected net with Schläfli symbol of (4²³?·?6¹³)(4³). The solid 1 exhibits high thermal stability and shows strong blue fluorescence emission at 410?nm in the solid state at ambient temperature.     

Synthesis and characterization of a new open-framework fluorinated gallium phosphite with three-dimensional intersecting channels

(C₄N₂H₁₂)[Ga₂F₃(HPO₃)₂(H₂PO₃)] 1 is a new open-framework fluorinated gallium phosphite obtained by mild hydrothermal synthesis using piperazine as template agent and characterized by single crystal X-ray diffraction (XRD), powder XRD, infra-red spectroscopy, inductively coupled plasma, thermogravimetric and elemental analyses. The three-dimensional (3D) anionic framework of compound 1 is constructed from two distinct motifs, a 1D tancoite chain and a single 4-ring (S4R) unit, which contains four intersecting channels running throughout the structure as 8, 12-member rings channels along to the a-axis and 12-member ring channels along the b- and c-axis, respectively. The well-ordered, diprotonated piperazine cations occupy all the channels, and interact with the fluorinated gallium-phosphite framework by strong hydrogen bonds.