Reversible Assembly and Disassembly of Metal-Organic Polyhedra: Towards Dimensionally Controlled Synthesis of Functional Porous Materials

• Applicant: Eunji Jin, Ph.D.
• Subject Area: Solid State and Surface Chemistry, Material Synthesis
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 557280007

Metal-Organic Polyhedra (MOPs) are a fascinating class of inorganic-organic materials. They offer internal porosity in the cage to encapsulate small molecules for gas storage, separation, catalysis, and even in medicine and environmental protection. The packing of MOPs in crystals is challenging to control. The project proposes a novel strategy for the reversible assembly of MOPs into dimensionally controlled network architectures and subsequent disassembly of these networks back into the original MOPs. New nanocages are synthesized from customized organic and inorganic building blocks through surface functionalization. These synthesized cage molecules are characterized using various techniques, such as DLS, NMR, MS etc. The reversible formation of covalent bonds will be studied using two approaches: 1) Photochemical reactions are explored to convert 0D nanocages into 3D frameworks. 2) Redox reactions such as disulfide formation are utilized for the dimensionally controlled polymerization of the MOPs. These transformations can be also performed through electrochemical methods. The kinetics of polymerization can be analyzed using electroanalytical techniques such as cyclic voltammetry. The resulting 2D and 3D frameworks are characterized with respect to their gas storage and adsorption properties. The reversible interconnection of MOPs into dimensionally controlled porous architectures poses enormous chances for the direct formation of porous materials as membranes, coatings and monoliths, even additive manufacturing as an important contribution for the development of environmental benign technologies in the future.

• DFG Programme: Research Grants