Targeting Diverse Bridging Motifs within Actinide Borosulfates and Establishing an Unconventional Structural...

The first actinide borosulfates, (UO₂)[B(SO₄)₂(SO₃OH)] (TSUBOS-1) and (UO₂)₂[B₂O(SO₄)₃(SO₃OH)₂] (TSUBOB-1), were synthesized solvothermally in oleum using UO₃. The classical borosulfate crystal structure of TSUBOS-1 is partially consistent with an established conventional hierarchy. Uranyl pentagonal bipyramids limit the anionic network linkages and isolate sulfate tetrahedra within the anionic network. Therefore, the classical one-dimensional chain established in the hierarchy does not fully describe the structure. The structure of TSUBOB-1 is the first actinide borosulfate that contains an unconventional borate-to-borate bridging mode (denoted B-O-B) and a zero-dimensional oxoanionic unit consisting of one sulfate tetrahedron that shares vertices with two B-O-B bridged borate tetrahedra that each share a vertex with two sulfate tetrahedra. As this structure departs from the existing structural hierarchy, a modified approach for understanding the unconventional borosulfate substructure and dimensionality is proposed, together with a new graphical notation. In the course of our synthesis experiments, a novel uranyl disulfate compound (UO₂)₂[(S₂O₇)(SO₃OH)₂] (TSUDS) was isolated and characterized. The structure of TSUDS is a framework consisting of uranyl pentagonal bipyramids and sulfate tetrahedra. Each uranyl pentagonal bipyramid is surrounded by five sulfate tetrahedra, two of which share a vertex creating a disulfate with a S-O-S bridging mode. The uranyl bipyramids are linked to one another via the singular sulfate or disulfate groups.