A Redox-Innocent Uranium(IV)-Quinoid Metal-Organic Framework

Abstract

Quinoid-based ligands constitute the most common class of redox-active ligands used to construct electrically conductive and magnetic metal-organic frameworks (MOFs). Whereas this chemistry is intensively explored for transition-metal and lanthanide ions, any related actinide compound has not received attention. In particular, the MOF chemistry of actinide ions in the lower oxidation states is underexplored. We herein report the synthesis, and structural and physical property characterization of a uranium(IV) quinoid-based MOF, [U(Cl2dhbq)2(H2O)2]·4H2O (1, Cl2dhbq2- = deprotonated 2,5-dichloro-3,6-dihydroxybenzoquinone). 1 is a rare example of a U(IV)-based coordination solid and the first material to incorporate bona fide reducible bridging ligands. Despite the anticipated thermodynamic driving force, no indications of valence tautomerism are evident from magnetometry, near-IR spectroscopy, and X-band electron paramagnetic resonance measurements. These initial results suggest that reduction potentials alone are insufficient as guidelines for the prediction of the occurrence of electron transfer in uranium-quinoid-based materials.