Functional metal-organic liquids.

For decades, the study of coordination polymers (CPs) and metal-organic frameworks (MOFs) has been limited primarily to their behavior as crystalline solids. In recent years, there has been increasing evidence that they can undergo reversible crystal-to-liquid transitions. However, their "liquid" states have primarily been considered intermediate states, and their diverse properties and applications of the liquid itself have been overlooked. As we learn from organic polymers, ceramics, and metals, understanding the structures and properties of liquid states is essential for exploring new properties and functions that are not achievable in their crystalline state. This review presents state-of-the-art research on the liquid states of CPs and MOFs while discussing the fundamental concepts involved in controlling them. We consider the different types of crystal-to-liquid transitions found in CPs and MOFs while extending the interpretation toward other functional metal-organic liquids, such as metal-containing ionic liquids and porous liquids, and try to suggest the unique features of CP/MOF liquids. We highlight their potential applications and present an outlook for future opportunities.

Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer.

We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)(CF3SO3)2] (1, L1 = 4,4'-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10-2 Pa·s at Tm which is six orders lower than that of ZIF-62 at Tm (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high Tm provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.