Fundamental aspects of the amorphous state of metal organic compounds: a solid state magnetic resonance approach

• Grant number: 22/02974-1
• Support Opportunities: Research Grants - Initial Project
• Start date: February 01, 2023
• End date: January 31, 2028
• Field of knowledge: Physical Sciences and Mathematics - Physics - Condensed Matter Physics
• Principal Investigator: Marcos de Oliveira Junior
• Grantee: Marcos de Oliveira Junior
• Host Institution: Instituto de Física de São Carlos (IFSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• City of the host institution: São Carlos
• Associated researchers: Andrea Simone Stucchi de Camargo Alvarez Bernardez ; Danilo Manzani ; Osvaldo Antonio Serra
• Associated research grant(s): 25/12521-2 - Synthesis and Characterization of Luminescent Composites Based on Fluorophosphate Glasses and Tricarboxylic Acid MOFs, AP.R
• Associated scholarship(s): 25/08252-6 - Development of a bioactive glass/lanthanide metal-organic framework composite for bioimaging applications, BP.PD; 25/12640-1 - Glass Formation and solid state NMR studies of Cd-, Pt-, B-, Li- , Cu- and Co-based zeolitic imidazole frameworks, BP.DR; 24/19256-0 - Synthesis and structural characterization of luminescent MOF crystal-glass composites for photonic applications, BP.DR; + associated scholarships 24/20837-7 - Exploration of Glass Formation in Single- and Mixed-Ligands Zeolitic Imidazole Frameworks, BP.MS; 24/07760-5 - Preparation and structural characterization of composites of MOFs and inorganic glasses, BP.IC; 24/03731-0 - Investigation of Structural Details of Amorphous Zeoltitic Imidazole Frameworks Obtained by Different Solid State Amorphization Methods, BP.IC; 23/07712-8 - Solid State NMR And EPR Characterization of metallic Coordination Environments in Amorphous Zeolitic Imidazole Frameworks, BP.MS - associated scholarships

Abstract

The main objective of this proposal is to catalyze a new line of research within the Magnetic Resonance Group of IFSC-USP. The research will focus on the structural characterization of non-crystalline Metal-Organic Frameworks (MOFs), Coordination Polymers (CPs) and other Hybrid Materials. Great attention has been paid to research on MOFs since their discovery. Thanks to their chemical versatility and the possibility of permanent porosity (with the largest surface areas reported to date), these compounds are candidates for a variety of applications, such as gas storage, separation of molecular species, energy storage, catalysis, photonics, pharmaceuticals, among others. The vast majority of works on this field focus on the crystalline domain. However, in the last decade it has been noticed that many of the relevant properties of MOFs are not linked to their crystallinity. On the contrary, the transition to the amorphous domain provides a variety of advantages for these materials, such as the possibility of obtaining single monolithic morphology, absence of grain boundaries, presence of defects as functionalization pathways and size/shape flexibility. Since then, there has been a growing interest in amorphous structured MOFs, especially glass-forming ones. Research in this field is still on its early stages. There are many open questions regarding the understanding of the structure of these materials and the amorphization mechanisms. Due to its amorphous character, techniques widely used for the structural determination of crystalline materials, such as X-ray diffraction, cannot be applied. Solid state Nuclear Magnetic Resonance (NMR) spectroscopy is an excellent, and currently underexplored, tool for the characterization of local environments in such amorphous systems. To contribute to this field, we propose to carry out a detailed structure characterization of selected compositions, mainly using NMR and Electronic Paramagnetic Resonance (EPR) techniques, in particular employing technical approaches not yet applied to amorphous MOFs and CPs. These techniques can provide local information about (i) the structure of organic ligands; (ii) the chemical environment of the metallic sites; (iii) the interaction between organic and inorganic components; and (iv) the distribution of ligands at the metal center (in the case of mixed ligand compounds). Along with this goal, we will form human resources by training undergraduate and graduate students with multidisciplinary concepts of solid state NMR and EPR and materials science. Finally, at more advanced stage, the project will explore new compositions of vitreous MOFs and composites, focusing mainly on materials with promising luminescent properties, for future photonic applications. (AU)

Scientific publications

(7)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

FLORES, ALI F. GARCIA; MUNEVAR, JULIAN; DE OLIVEIRA, MARCOS; RETTORI, CARLOS; URBANO, RICARDO R.; DE QUEIROZ, THIAGO B.. Relaxation Processes in Rare-Earth-Doped a-NaYF₄ Nanoparticles by Nuclear Magnetic Resonance Spectroscopy. Journal of Physical Chemistry C, v. 127, n. 37, p. 11-pg., 2023-09-11. (22/02974-1, 19/09673-4, 20/13466-1, 17/10581-1)

DA SILVA, LEANDRO OLIVETTI ESTEVAM; RIVERA, V. A. G.; FALCI, RODRIGO; MESSADDEQ, YOUNES; DE OLIVEIRA JUNIOR, MARCOS; MANZANIA, DANILO. Fluorine alkaline earth (MgF2, CaF2, SrF2, BaF2) influence on thermal, structural, and luminescent properties of Eu3+-doped niobium phospho-fluoride glass. Materials Research Bulletin, v. 185, p. 12-pg., 2025-01-11. (22/01762-0, 13/07793-6, 21/08111-2, 23/05994-6, 22/02974-1, 19/16115-8)

MARCOS, FRANCIELLE CANDIAN FIRMINO; COSTA, MARIA JOSE FONSECA; CATUZO, GABRIEL L.; DE MORAES, DANIEL ANGELI; DE OLIVEIRA JR, MARCOS; MASTELARO, VALMOR ROBERTO; ASSAF, JOSE MANSUR; GIUDICI, REINALDO; ASSAF, ELISABETE MORREIRA. Supported Cu catalysts on UiO-66 toward enhanced methanol selectivity by CO₂ hydrogenation: Effect of Cu loading. JOURNAL OF CATALYSIS, v. 427, p. 9-pg., 2023-11-01. (17/08293-8, 22/02974-1, 20/15230-5)

MELO, G. H. A.; DANTAS, N. F.; MUNIZ, F. R.; MANZANI, D.; DE OLIVEIRA JR, M.; PEDROCHI, F.; STEIMACHER, A.. The effect of ZnO on the structural and radiation shielding properties in borophosphate glasses. Journal of Non-Crystalline Solids, v. 618, p. 13-pg., 2023-07-31. (22/02974-1, 21/08111-2)

HERR, KEVIN; HOEFLER, MARK, V; HEISE, HENRIKE; AUSSENAC, FABIEN; KORNEMANN, FELIX; ROSENBERGER, DAVID; BRODRECHT, MARTIN; DE OLIVEIRA JR., MARCOS; BUNTKOWSKY, GERD; GUTMANN, TORSTEN. Biradicals based on PROXYL containing building blocks for efficient dynamic nuclear polarization in biotolerant media. JOURNAL OF MAGNETIC RESONANCE OPEN, v. 20, p. 11-pg., 2024-09-01. (22/02974-1, 13/07793-6)

DE ASSIS, RENAN GABRIEL; DE OLIVEIRA JUNIOR, MARCOS; ESCOTE, MARCIA TSUYAMA; PINHEIRO, CARLOS BASILIO; ACUNA, JOSE JAVIER SAEZ; FERREIRA, FABIO FURLAN; PEDROZA, LUANA SUCUPIRA; BROCHSZTAIN, SERGIO; DE QUEIROZ, THIAGO BRANQUINHO. Preparation and Characterization of a Disilylated Naphthalenediimide Molecular Crystal: Perspectives for Organosilica Mesoporous Materials. ACS APPLIED ENGINEERING MATERIALS, v. 2, n. 7, p. 11-pg., 2024-07-08. (23/01502-1, 21/07694-4, 13/07793-6, 17/10292-0, 23/08771-8, 22/02974-1, 20/13466-1)

TAYAMA, GABRIEL TOSHIAKI; COSTA, BEATRIZ HELENA; CAIXETA, FABIO JOSE; MURBACK FILHO, RENATO PEREIRA; DE OLIVEIRA JUNIOR, MARCOS; ELIAS E SILVA, LUCAS TOTH; MESSADDEQ, YOUNES; SANTAGNELI, SILVIA HELENA. Luminescent Eu³⁺ doped silicate-aluminum-borate hybrid materials obtained by photopolymerization of sol-gel resins. Journal of Sol-Gel Science and Technology, v. N/A, p. 13-pg., 2025-07-04. (23/07712-8, 13/07793-6, 22/02974-1)