Qinhe Pan

A crystalline germanate with mesoporous 30-ring channels.

A novel germanate |C(6)N(2)H(18)|(30)[Ge(9)O(18)X(4)](6)[Ge(7)O(14)X(3)](4)[Ge(7)O(14.42)X(2.58)](8)[GeX(2)](1.73) (X = OH, F) with 30-ring channels built from Ge(7)O(14)X(3) (Ge(7)) and Ge(9)O(18)X(4) (Ge(9)) clusters was obtained under solvothermal conditions. It has a mesoporous pore of 13.0 x 21.4 A(2), which represents the largest pore ring found in crystalline open-framework materials. The framework can be described as a 3-D net structure and viewed as introducing Ge(7) and Ge(9) clusters into the 4,8-heterocoordinated csq net.

A Germanate Built from a 68126 Cavity Cotemplated by an (H2O)16 Cluster and 2‐Methylpiperazine

Totally tubular: A new tubular germanate is cotemplated by 2-methylpiperazine and an (H2O)16 cluster in a hydro(solvo)thermal synthesis. The germanate features a large, highly symmetric 68126 cavity (see picture; yellow sphere) built from 12 Ge7X19 (X=O, OH, F) clusters (GeX6 red, GeX5 yellow, GeX4 green).

Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks.

A 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V(3)P(3)BO(19)](5)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.

Synthesis, structure and magnetic property of a new organo-templated mixed-valent iron(II, III) borophosphate

A new layered iron borophosphate (C4N3H16)(C4N3H15)0.5[Fe2B4P7O26(OH)4] (denoted FeBPO-CJ28), with a novel B/P ratio of 4/7 and mixed-valent iron(II, III) was prepared under mild hydrothermal conditions in the presence of diethylenetriamine (DETA) as the template. Its crystal structure was determined by single-crystal X-ray diffraction (triclinic, P (No. 2), a = 8.9568(3) A, b = 9.8717(3) A, c = 17.9905(5) A, α = 102.510(2)°, β = 92.343(2)°, γ = 100.403(2)°, V = 1522.10(8) A3, and Z = 2). The structure comprises unprecedented anionic double layers 2∞{[Fe2B4P7O26(OH)4]4−} with one-dimensional 8-ring channels along the [110] direction, which are made up of FeO6, BO4, PO4 and HPO4 polyhedral units. Such double layers parallel to the ab plane are connected by inter-layer hydrogen bonds forming the three-dimensional (3D) supramolecular open framework with pseudo 10-ring channels along the [110] direction. Protonated DETA cations locate in the 8-ring channels and pseudo 10-ring channels to compensate the negative charge of the anionic framework. The structure is featured by a new fundamental building unit (FBU) [B4P7O26(OH)4], which is the largest one of the borophosphate anionic partial structures. The compound is further characterized by powder XRD, ICP, CHN, TGA and Mossbauer spectroscopy analysis. The magnetic measurement reveals that FeBPO-CJ28 exhibits ferrimagnetic behavior below 9.6 K with a hysteresis loop at 2 K (HC = 2800 Oe, MR = 0.21 µB).

Syntheses and Characterizations of Transition-Metal-Substituted Aluminophosphate Molecular Sieves |(C3N2H5)8|[M8Al16P24O96] (M = Co, Mn, Zn) with Zeotype LAU Topology

Three transitional-metal-substituted aluminophosphate molecular sieves, |(C3N2H5)8|[M8Al16P24O96] (denoted MAPO-LAU, M = Co, Mn, Zn), have been synthesized under solvothermal conditions in the presence of imidazole as the structure-directing agent. Their structures are determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, thermogravimetric, and diffuse reflectance spectroscopy (UV-vis) analyses. The structure of MAPO-LAU is based on the strict alternation of MO4/AlO4 tetrahedra and PO4 tetrahedra through vertex oxygen atoms. Their frameworks are analogous to the zeotype LAU structure in which 33% of the aluminum sites are replaced by transitional-metal ions. The protonated imidazole cations resided in the 10-ring channels. These compounds show photoluminescent properties due to the existence of imidazole molecules in the structures. Magnetic measurements reveal that there is very weak antiferromagnetic interaction among the metal centers of MnAPO-LAU.

Two novel Zn‐MOFs: structures and characterization

Two novel three-dimensional Zn-MOFs (zinc metal-organic frameworks), Zn(5)(μ(3)-OH)(BTC)(3)(Phen)(4)·5H(2)O (denoted as HUT-11) and Zn(4)(μ(4)-O)(BTC)(2)(Phen)(2)·4H(2)O (denoted as HUT-12), have been synthesized by metal-ligand-directed assembly under hydrothermal conditions. Here, BTC and Phen are denoted as 1,3,5-benzenetricarboxylate and phenanthroline. HUT-11 contains two kinds of secondary building units (SBUs), Zn(3)(μ(3)-OH)(COO)(5) clusters and Zn(2)(COO)(4) clusters. This material exhibits a new three-dimensional (3,4,5)-connected topology with the Schläfli symbol (4·6·8)(2)(4·8(2))(4·6(4)·8(5))(4(2)·6(2)·8(2)). Two perpendicular planes cross at five coordinated Zn1-Zn3-Zn5 nodes, giving a new three-dimensional network. HUT-12 is composed of Zn(4)(μ(4)-O)(COO)(6) clusters as the secondary building units and displays a two-dimensional (3,6)-connected TiS(2) related net topology with the Schläfli symbol (4(2)·6)(4(4)·6(2)·8(8)·10). Both MOFs show blue light emission and a high thermal stability above 673 K.