08 February 2024 | Minhyuk Kim, Hwa-Sub Lee, Dong-Hyun Seo, Sung June Cho, Eun-chae Jeon & Hoi Ri Moon
A study reports the creation of carboxylate-based metal-organic framework (MOF) glasses through melt-quenching of crystalline MOFs containing Mg²⁺ or Mn²⁺ ions with an aliphatic carboxylate ligand, adipate. These MOFs have lower melting temperatures (284 °C for Mg and 238 °C for Mn) compared to zeolitic-imidazolate framework (ZIF) glasses, and exhibit superior mechanical properties, including higher hardness and elastic modulus. The low melting temperatures are attributed to the flexibility and low symmetry of the aliphatic carboxylate ligand, which increases the entropy of fusion and reduces the enthalpy of fusion. The research demonstrates that these MOF glasses can be formed by controlling the enthalpy and entropy of fusion during thermal transitions. The glasses retain the connectivity between carboxylate and metal ions, and show high glass-forming ability, indicating their capacity to vitrify without recrystallization. The mechanical properties of the glassy MOFs were characterized using nanoindentation, revealing higher hardness and elastic modulus compared to reported coordination polymer glasses. The study also explores the thermal behavior of different MOF systems, showing that the melting of C-Mg-adp and C-Mn-adp is influenced by the entropy contribution of the aliphatic ligand and the low crystal field stabilization energy of the metal ions. The results suggest that carboxylate-based MOF glasses have potential applications in various fields due to their unique mechanical and thermal properties. The study provides insights into the structure-property relationships of MOF glasses and offers a promising approach for the development of meltable MOF structures based on carboxylate linkers.A study reports the creation of carboxylate-based metal-organic framework (MOF) glasses through melt-quenching of crystalline MOFs containing Mg²⁺ or Mn²⁺ ions with an aliphatic carboxylate ligand, adipate. These MOFs have lower melting temperatures (284 °C for Mg and 238 °C for Mn) compared to zeolitic-imidazolate framework (ZIF) glasses, and exhibit superior mechanical properties, including higher hardness and elastic modulus. The low melting temperatures are attributed to the flexibility and low symmetry of the aliphatic carboxylate ligand, which increases the entropy of fusion and reduces the enthalpy of fusion. The research demonstrates that these MOF glasses can be formed by controlling the enthalpy and entropy of fusion during thermal transitions. The glasses retain the connectivity between carboxylate and metal ions, and show high glass-forming ability, indicating their capacity to vitrify without recrystallization. The mechanical properties of the glassy MOFs were characterized using nanoindentation, revealing higher hardness and elastic modulus compared to reported coordination polymer glasses. The study also explores the thermal behavior of different MOF systems, showing that the melting of C-Mg-adp and C-Mn-adp is influenced by the entropy contribution of the aliphatic ligand and the low crystal field stabilization energy of the metal ions. The results suggest that carboxylate-based MOF glasses have potential applications in various fields due to their unique mechanical and thermal properties. The study provides insights into the structure-property relationships of MOF glasses and offers a promising approach for the development of meltable MOF structures based on carboxylate linkers.