Actinide polyrotaxane compounds, which represent a type of topologically unique actinide compounds, definitely show different assembly modes of actinide ions with supramolecular systems compared to other transition metal and lanthanide metal ions. Our group conducted the related studies of actinide-organic rotaxane compounds and we have succeeded in the preparation the first case of uranyl-organic rotaxane compounds with a unique ‘dragon-like’ twist under hydrothermal conditions, which is induced by the specific coordination pattern of uranium and stabilized by hydrogen bonding between the η1-mode carboxylate group and adjacent methylene moieties of CB[6]. As the unprecedented extension of actinide-rotaxane complexes from uranium to transuranium, we also reported the first crystal structure of neptunium-rotaxane complex, of which the intriguing interwoven neptunium(V)-rotaxane coordination network incorprating mechanically-interlocked [c2]daisy chain unit is promoted by simultaneous coordination of cucurbituril (CB6) and carboxyl groups from axle molecules in pseudorotaxane to NpV. The exploration of this new type of structurally unique actinide-bearing supramolecular architectures has a stimulative effect on the pursuit of other special ligands for actinides and new types of actinide entangled structures with more complex assembly modes. Simple non-extended transuranium polyrotaxane compounds formed by volatilization or diffusion method are also expected in the future.

Actinide polyrotaxane compounds: From structural diversity to inclusion effect

2019 Spring National Meeting

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