Unusual metal–organic framework topology and radiation resistance through neptunyl coordination chemistry

A Np(V) neptunyl metal-organic framework (MOF) with rod-shaped secondary building units was synthesized, characterized, and irradiated with γ rays. Single-crystal X-ray diffraction data revealed an anionic framework containing infinite helical chains of actinyl-actinyl interaction (AAI)-connected neptunyl ions linked together through tetratopic tetrahedral organic ligands (NSM). NSM exhibits an unprecedented net, demonstrating that AAIs may be exploited to give new MOFs and new topologies. To probe its radiation stability, we undertook the first irradiation study of a transuranic MOF and its organic linker building block using high doses of γ rays. Diffraction and spectroscopic data demonstrated that the radiation resistance of NSM is greater than that of its linker building block alone. Approximately 6 MGy of irradiation begins to induce notable changes in the long- and short-range order of the framework, whereas 3 MGy of irradiation induces total X-ray amorphization and changes in the local vibrational bands of the linker building block.