Heterometallic uranyl-organic frameworks incorporating manganese and copper: Structures, ammonia sorption and magnetic properties

Incorporating transition metal ions into uranyl phosphonate frameworks can bring not only new structure types but also interesting physical or chemical properties. Herein we report two heterometallic uranyl carboxyphenylphosphonates, namely, [Cu2(UO2)3(2-pmbH)2(2-pmb)2(H2O)4]·2H2O (1) and [Mn3(UO2)6(2-pmb)6(H2O)8]·10H2O (2) [2-pmbH3 = 2-(phosphonomethyl)benzoic acid]. Compound 1 shows a two-dimensional layered structure in which uranyl-PO3 chains are linked by {Cu2O2} dimers. Within the uranyl-PO3 chain, {UO6} tetragonal bipyramids and edge-sharing dimers of {UO7} pentagonal bipyramids are connected by edge-sharing {PO3C} tetrahedra. Compound 2 possesses a unique 3D open framework structure, where the Mn-layers are pillared by uranyl-PO3 chains. The uranyl-PO3 chain in 2 is very different from that in 1, which contains trimers of edge-sharing {UO7} and {UO8} polyhedra and {PO3C} linkages. While the Mn-layer consists of chains of {MnO6} octahedra bridged alternatively by carboxylate and phosphonate groups, which are inter-connected by organic moieties of 2-pmb3-. The thermally activated sample of 2 displays strong adsorption capability toward NH3. Magnetic studies revealed dominant antiferromagnetic interactions between the metal centers in both compounds.