Directed assembly of hybrid architectures containing lanthanide or actinide elements is of interest considering applications ranging from sensing to spent nuclear fuel stewardship. f block elements display a range of oxidation states, varying emissive properties and coordination geometries unique to this region of the periodic table. Moreover, the tendency for ions of these elements to hydrolyze (Ln(III) and U(VI) in particular), gives rise to rich suites of oligomeric building units from which to assemble topologies of interest. The latter may be viewed as an asset and a liability. On the plus side, one may anticipate diverse topologies, yet not knowing which building units will manifest themselves in the solid state prevents systematic study and delineation of rules governing assembly. We have developed an approach of 'restricted speciation' wherein reaction conditions, either high-halide media or through the use of chelating ligands, promote the formation of a single molecular species. These species, [UO2X4(H2O)n]2- (X= Cl, Br, NCS; n=0,1) or [Ln(terpy)(p-XBA)3] (p-XBA = p-halobenzoic acid, X =Cl, Br and I) are then assembled into extended architectures via non-covalent interactions through halogens at their periphery. Presented will be an overview of results from both Ln and An families, along with an early attempt at ranking the strengths of non-covalent interactions.

Hybrid materials from the f-block: Tips and tricks for directing supramolecular assemblies

247th National Meeting (2014)

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