Colossal negative thermal expansion in a cucurbit[8]uril-enabled uranyl-organic polythreading framework via thermally induced relaxation

Abstract

It is an ongoing goal to achieve the effective regulation of the thermal expansion properties of materials. In this work, we propose a method for incorporating host–guest complexation into a framework structure and construct a flexible cucurbit[8]uril uranyl-organic polythreading framework, U₃(bcbpy)₃(CB8). U₃(bcbpy)₃(CB8) can undergo huge negative thermal expansion (NTE) and has a large volumetric coefficient of −962.9 × 10⁻⁶ K⁻¹ within the temperature range of 260 K to 300 K. Crystallographic snapshots of the polythreading framework at various temperatures reveal that, different from the intrinsic transverse vibrations of the subunits of metal–organic frameworks (MOFs) that experience NTE via a well-known hinging model, the remarkable NTE effect observed here is the result of a newly-proposed thermally induced relaxation process. During this process, an extreme spring-like contraction of the flexible CB8-based pseudorotaxane units, with an onset temperature of ∼260 K, follows a period of cumulative expansion. More interestingly, compared with MOFs that commonly have relatively strong coordination bonds, due to the difference in the structural flexibility and adaptivity of the weakly bonded U₃(bcbpy)₃(CB8) polythreading framework, U₃(bcbpy)₃(CB8) shows unique time-dependent structural dynamics related to the relaxation process, the first time this has been reported in NTE materials. This work provides a feasible pathway for exploring new NTE mechanisms by using tailored supramolecular host–guest complexes with high structural flexibility and has promise for the design of new kinds of functional metal–organic materials with controllable thermal responsive behaviour.