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000840125 1001_ $$0P:(DE-Juel1)165796$$aHao, Yucheng$$b0$$ufzj
000840125 245__ $$aPorous Uranyl Borophosphates with Unique Three-Dimensional Open-Framework Structures
000840125 260__ $$aWashington, DC$$bAmerican Chemical Society$$c2017
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000840125 520__ $$aTwo novel alkali-metal uranyl borophosphates have been prepared and characterized for the first time, namely, K5(UO2)2[B2P3O12(OH)]2(OH)(H2O)2 and K2(UO2)12[B(H2PO4)4](PO4)8(OH)(H2O)6 denoted as KUPB1 and KUPB2, respectively. KUPB1 was obtained hydrothermally at 220 °C and crystallizes in a monoclinic structure in the chiral space group P21. The unit cell parameters of KUPB1 are a = 6.7623(2) Å, b = 19.5584(7) Å, c = 11.0110(4) Å, α = γ = 90°, β = 95.579(3)°, and V = 1449.42(8) Å3. It features a unique three-dimensional (3D) open-framework structure, composed of two corner-sharing linked one-dimensional (1D) anionic borophosphates (BP), [B2P3O13]5–, along the a axis and uranyl phosphate (UP), [(UO2)(PO4)3]7–, chains along the c axis, further bridged by PO4 tetrahedra. Multi-intersectional channels can be observed within the structure, in which the largest 11-ring (11-R) tunnel size is ∼7.0 Å × 8.8 Å. Its simplified framework can be described as a new 4-nodal net topological type with a point symbol of {4.84.10}{42.6}2{43.62.83.102}{82.10}. By modification of the synthetic conditions of KUPB1 through an increase in the amount of H3BO3 as flux 4-fold and a reduction of water as the reaction medium, the novel compound KUPB2 is generated. The unit cell parameters of KUPB2 are a = b = 21.8747(3) Å, c = 7.0652(2) Å, α = β = γ = 90°, and V = 3380.72(12) Å3. KUPB2 crystallizes in a tetragonal structure in the polar space group I4̅2m, and its structure is based on a highly complex 3D framework, {(UO2)12[B(PO4)4](PO4)8}9–, in which 1D 8-R UP [(UO2)(PO4)]− tubes can be observed along the c axis. The [(UO2)(PO4)]− tubes consist of three uranyl chains along the c axis, which are linked alternately by [PO4]3– tetrahedra. Those isolated 1D [(UO2)(PO4)]− tubes are further bridged through [(UO2)4B(PO4)4]− clusters, forming an exceptional 3D open-framework structure. Its simplified cation network is a new 5-nodal net topological type such as {32.43.5.62.7.8}8{34.45.54.62}8{4.62.83}4{42.6}4{44.62}. Their facile hydrothermal synthetic routes, porous structure topology, thermal stability, and Raman spectroscopy properties are reported and discussed.
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000840125 7001_ $$0P:(DE-HGF)0$$aMurphy, Gabriel L.$$b1
000840125 7001_ $$0P:(DE-Juel1)130324$$aBosbach, Dirk$$b2$$ufzj
000840125 7001_ $$0P:(DE-Juel1)130383$$aModolo, Giuseppe$$b3$$ufzj
000840125 7001_ $$0P:(DE-HGF)0$$aAlbrecht-Schmitt, Thomas E.$$b4
000840125 7001_ $$0P:(DE-Juel1)144426$$aAlekseev, Evgeny$$b5$$eCorresponding author$$ufzj
000840125 773__ $$0PERI:(DE-600)1484438-2$$a10.1021/acs.inorgchem.7b01443$$gVol. 56, no. 15, p. 9311 - 9320$$n15$$p9311 - 9320$$tInorganic chemistry$$v56$$x1520-510X$$y2017
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