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Abstract: The three new framework Rb uranyl phosphates and arsenates with anionic parts based on different type of polymeric anions have been prepared by high-temperature solid-state reactions: Rb4[(UO2)6(P2O7)4(H2O)] (1), Rb2[(UO2)3(P2O7)(P4O12)] (2), Rb[(UO2)2(As3O10)] (3). The crystal structures of the synthesized compounds have been solved by direct methods: 1—monoclinic P21/c, a=9.672(1)Å, b=12.951(1)Å, c=32.231(3)Å, β=90.116(4)°, V=4037.3(6)Å3, Z=4, R 1=0.0926 for 6351 unique reflections with ; 2—monoclinic, P21/c, a=6.791(1)Å, b=16.155(3)Å, c=19.856(4)Å, β=97.48(5)°, V=2159.8(7)Å3, Z=4, R 1=0.0286 for 3617 unique reflections with ; 3—orthorhombic, Pbcn, a=10.558(1)Å, b=11.037(1)Å, c=11.464(1)Å, V=1335.9(2)Å3, Z=4, R 1=0.0489 for 1384 unique reflections with . The structures of title are compounds based on 3D negatively charged frameworks with chemical compositions [(UO2)6(P2O7)4(H2O)]4− in 1, [(UO2)3(P2O7)(P4O12)]2− in 2 and [(UO2)2(As3O10)]− in 3. These negative charges are compensated by rubidium cations which are in the channels of 1 and closed cages in structures of 2 and 3. The channels in 1 are directed along the a direction and have minimum dimensions ∼5Å×6Å. This is the first example of porosity generation through solid state synthesis in uranyl compounds. For the first time in uranium chemistry polymeric anionic groups P4O12 and As3O10 were observed in structure of 2 and 3. [Copyright &y& Elsevier]

K[AsW2O9], prepared by high-temperature solid-state reaction, is the first member of the arsenate–tungsten bronze family. The structure of K[AsW2O9] is based on a 3-dimensional (3D) oxotungstate–arsenate framework with the non-centrosymmetric P212121 space group, a=4.9747(3)Å, b=9.1780(8) Å, c=16.681(2) Å. The material was characterized using X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Raman and infrared (IR) spectroscopic techniques. The results of DSC demonstrate that this phase is stable up to 1076K. Second harmonic generation (SHG) measurements performed on a powder sample demonstrate noticeable (0.1 of LiIO3) non-linear optical (NLO) activity. [ABSTRACT FROM AUTHOR]