Glass Formation and solid state NMR studies of Cd-, Pt-, B-, Li- , Cu- and Co-based zeolitic imidazole frameworks

• Grant number: 25/12640-1
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: August 01, 2025
• End date: July 31, 2028
• Field of knowledge: Physical Sciences and Mathematics - Physics - Condensed Matter Physics
• Principal Investigator: Marcos de Oliveira Junior
• Grantee: Renato Pereira Murback Filho
• Host Institution: Instituto de Física de São Carlos (IFSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Associated research grant: 22/02974-1 - Fundamental aspects of the amorphous state of metal organic compounds: a solid state magnetic resonance approach, AP.PNGP.PI

Abstract

Metal-organic frameworks (MOFs) are hybrid materials, where inorganic clusters are interconnected by organic linkers, giving origin to two- or three-dimensional porous networks. Research regarding MOF traditionally focus on the crystalline domain. However, monolithic or powder crystals are difficult to handle, limiting industrial performance. For this reason, amorphous systems derived from MOFs are gaining increasing attention from the scientific community. Among them, MOF-glasses have clear advantage due to the processability from the molten state, allowing shaping possibilities which are not possible with traditional MOFs. Recent ultra-high field 67Zn NMR research has shown for the first time that the larger structural differences between glasses and their crystalline counterparts resides on the metallic-center's environment. Therefore, in this project we propose to explore the substitution of Zn in Zeolitic Imidazole Frameworks (ZIFs) by more favorable Nuclear Magnetic Resonance (NMR) observables, such as 11B, 7/6Li, 113Cd and 195Pt or Electron Paramagnetic Resonance (EPR) active ones, Co2+ and Cu2+. A complete study will be performed in order to characterize the metal coordination environment, the structure of the organic ligands and the connectivity between these species. The structural information obtained on glasses will be compared with fully or partially crystallized systems to give additional insight about the glass formation mechanisms in ZIFs.