Bouquet-like uranium-containing selenotungstate consisting of two different Keggin-/Anderson-type units with excellent photoluminescence quantum yield

We present the synthesis,characterization and photoluminescence properties of uranium-containing selenotungstate,[(UO_(2))_(3)(SeO_(3))_(3)Na_(5)(H_(2)O)_(6)(SeW_(6)O_(21))(SeW_(9)O_(33))_(3)]^(21–),which was isolated by a one-pot reaction of uranium nitrate with sodium tungstate and sodium selenite in a pH 5.2 aqueous solution at 90°C.In this study,the effect of the introduction of lone-electron pair containing heteroatoms on the structure is demonstrated,a three-layered heterometallic{Se_(3)U_(3)Na_(5)}cluster is encapsulated by two different anionic building block units:three trivacant Keggin{B-α-Se W_(9)O_(33)}and one Anderson{SeW_(6)O_(21)}.To our knowledge,the{Se_(3)U_(3)Na_(5)}cluster has never been observed in the polyoxometalate chemistry.The solidstate photoluminescence properties and lifetime decay behaviours of the title compound(1)have been measured at room temperature,and the photoluminescence spectrum displays the characteristic emission bands of corresponding uranyl cations.In addition,the photoluminescence quantum yield of 1 is 72%,which is almost three times that of starting material UO_(2)(NO_(3))_(2)·6H_(2)O(27%).By using this strategy,we envision that an increasing number of assemblies with‘open’clusters may be designed and obtained,in which the exposed oxygen atoms show strong affinity towards metal ions,providing new opportunities to generate bigger clusters or to tune existing properties.

Two Dawson-type U(Ⅵ)-containing selenotungstates with sandwich structure and its high-efficiency catalysis for pyrazoles

Two novel uranium-containing selenotungstates Na_(3)[H_(19)(UO_(2))_(2)(μ_(2)-O)(Se_(2)W_(14)O_(52))_(2)]·41 H_(2)O(U_(2))and(NH_(4))_(10)[H_(4)(SeO)_(2)(UO_(2))_(2)(H_(2)O)_(2)(H_(2)Se_(2)W_(14)O_(52))(Se_(2)W_(14)O_(52))]·66 H_(2)O(Se_(2)U_(2))based on the{Se_(2)W_(14)O_(52)}unit were successfully prepared and fully characterized.To our knowledge,the uranium is firstly introduced into the selenotungstates.Moreover,it is notable that U_(2)exhibits excellent Lewis acid-base catalytic activities in the condensation cyclization of sulfonyl hydrazides with diketones to synthesize polysubstituted pyrazoles.All the desired products were obtained in moderate to good yields(up to 99%).

Structural Chemistry of Heteroselenometallic Clusters

About forty heterobimetallic clusters with selenotungstate or se-lenomolybdate showing ten structural types of linear, butterfly, cubane-like, defective-cubane, planar and cage etc. are systematically classified and summarized, and severalsuggestions were proposed, which might be useful for further research on structuralchemistry of heteroselenometallic clusters.