Network-Forming Liquids from Metal–Bis(acetamide) Frameworks with Low Melting Temperatures

Molten phases of metal–organic networks offer exciting opportunities for using coordination chemistry principles to access liquids and glasses with unique and tunable structures and properties. Here, we discuss general thermodynamic strategies to provide an increased enthalpic and entropic driving force for reversible, low-temperature melting transitions in extended coordination solids and illustrate this approach through a systematic study of a series of bis(acetamide)-based networks with record-low melting temperatures. The low melting temperatures of these compounds are the result of weak coordination bonds, conformationally flexible bridging ligands, and weak electrostatic interactions between spatially separated cations and anions, which collectively reduce the enthalpy and increase the entropy of fusion. Through a combination of crystallography, spectroscopy, and calorimetry, enthalpic trends are found to be dictated by the strength of coordination bonds and hydrogen bonds within each compound, while entropic trends are strongly influenced by the degree to which residual motion and positional disorder are restricted in the crystalline state. Extended X-ray absorption fine structure (EXAFS) and pair distribution function (PDF) analysis of Co(bba)3[CoCl4] [bba = N,N′-1,4-butylenebis(acetamide)], which features a record-low melting temperature for a three-dimensional metal–organic network of 124 °C, provide direct evidence of metal–ligand coordination in the liquid phase, as well as intermediate- and extended-range order that support its network-forming nature. In addition, rheological measurements are used to rationalize differences in glass-forming ability and relaxation dynamics. These results provide new insights into the structural and chemical factors that influence the thermodynamics of melting transitions of extended coordination solids, as well as the structure and properties of coordination network-forming liquids.