The reaction of AgCN with UO2, 4,4'-bipy, and phosphoric acid in water at 160 degrees C under autogeneously generated pressure results in the formation of [Ag(4,4'-bipy)](2)[(UO2)(2)H-3(PO4)(3)] (AgUP-1). Ag(2,2'-bipy)(UO2)(2)(HPO4)(PO4) (AgUP-2) has been prepared from the hydrothermal reaction (at 180 degrees C) of KAg(CN)(2) with UO2(C2H3O2)(2)center dot 2H(2)O and 2,2'-bipy. [Zn(2,2'-bipy)](2)[UO2(HPO4)(3)] (ZnUP-1) was isolated from the hydrothermal reaction Of UO2, 2,2'-bipyridyl, Zn(CN)(2), and H3PO4. Single crystal X-ray diffraction experiments reveal that the structure of AgUP-1 consists of (2)(infinity)[(UO2)(2)H-3(PO4)(3)](2-) expanded autunite-like layers in the [ac] plane, separated by (1)(infinity)[Ag(4,4'-bipy)](+) chains of two-coordinate Ag+ bridged by 4,4'-bipy. The structure of AgUP-2 is composed of chains of edge-sharing UO7 pentagonal bipyramids that are linked by phosphate anions into (2)(infinity)[(UO2)(2)(HPO4)(PO4)](1-) sheets with the beta-uranophane topology that extend in the [ab] plane. Both sides of the sheets are decorated by [Ag(2,2'-bipy)](+) units, where the Ag+ cations are found in distorted trigonal planar environments. The structure of ZnUP-1 is 1D and consists Of UO7 pentagonal bipyramids that are connected by phosphate anions that also bind four-coordinate zinc(II) to the periphery of the chains and five-coordinate zinc within the chains. Intense fluorescence from these compounds was observed.