Syntheses, Crystal Structures, and Nonlinear Optical Activity of Cs2Ba[AnO2(C2H5COO)3]4 (An = U, Np, Pu) and Unprecedented Octanuclear Complex Units in KR2(H2O)8[UO2(C2H5COO)3]5 (R = Sr, Ba)статья
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Аннотация:X-ray diffraction was applied to the elucidation of crystal structures of single crystals of Cs2Ba[AnO2(C2H5COO)3]4, where An = U(I), Np(II), Pu(III), and KR2(H2O)8 [UO2(C2H5COO)3]5, where R = Sr(IV), Ba (polymorphs V-a and V-b). Isostructural cubic crystals I−III are constructed of typical mononuclear anionic complex units [AnO2(C2H5COO)3]− and charge-balancing Cs and Ba cations.
Features of actinide contraction in the six U−Np−Pu isostructural series known to date are analyzed. In crystal structures of IV and V two typical complexes [UO2(C2H5COO)3]− bind with a hydrated
Sr or Ba cation to form the rare trinuclear neutral complex unit {R(H2O)4[UO2(C2H5COO)3]2}, where R = Sr, Ba. Two such trinuclear units and one typical mononuclear unit further bind with a K cation to form the unprecedented octanuclear neutralcomplex unit K[UO2(C2H5COO)3]{R(H2O)4[UO2(C2H5COO)3]2}2. Peculiarities of noncovalent interactions in crystal structures of the two polymorphs
are revealed using Voronoi−Dirichlet tessellation. The nonlinear optical activity of noncentrosymmetric crystals I was estimated by its ability for second harmonic generation.