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Magnetic Resonance Techniques for the Study of Structure/Property Correlations in Photonic Glassy and Glass Ceramic Materials

Grant number: 13/23490-3
Support type:Scholarships in Brazil - Post-Doctorate
Effective date (Start): April 01, 2014
Effective date (End): February 27, 2018
Field of knowledge:Physical Sciences and Mathematics - Physics - Condensed Matter Physics
Principal researcher:Hellmut Eckert
Grantee:Marcos de Oliveira Junior
Home Institution: Instituto de Física de São Carlos (IFSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
Associated research grant:13/07793-6 - CEPIV - Center for Teaching, Research and Innovation in Glass, AP.CEPID
Associated scholarship(s):15/04063-2 - Coordination environments of rare-earth ions in photonic glasses analyzed by pulsed electron paramagnetic resonance techniques, BE.EP.PD


Transition Metal and rare-earth ion doped glasses and glass-ceramics are viewed as the new generation of luminescent photonic materials. Besides having superior thermal and mechanical properties than crystals, these materials can incorporate higher concentrations of doping ions and be fabricated at lower cost, in a larger variety of sizes and shapes. To optimize the luminescent properties of these materials, detailed structural information regarding the local environment of the rare-earth species is essential. While solid state nuclear magnetic resonance (NMR) is in general a promising tool for such purposes, unfortunately, the rare-earth ions themselves cannot be studied by NMR due to their paramagnetism. To overcome this difficulty, we propose to develop a comprehensive magnetic resonance strategy, comprising three complementary approaches: (i) NMR study of probe nuclei 45Sc, 89Y, 139La, 171Yb, and 175Lu, associated with diamagnetic "mimics" of the fluorescent species. (ii) analysis of the paramagnetic interactions of framework nuclei with the luminophores and (iii) examination of the magnetic dipolar interactions of the unpaired electrons with nearby nuclear spins, using electron spin echo envelope modulation (ESEEM) and electron nuclear double resonance (ENDOR) spectroscopies. This strategy will help to elucidate structural aspects of TM and RE doped glasses, such as: (i) the influence of the RE species on the structural organization of the glassy framework, (ii) the RE ion local environments, (iii) the connectivity of the RE ion species with the network former species, (iv) the overall spatial distribution of the rare-earth dopants, and (v) the structural aspects of the glass to glass ceramic transition.

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Scientific publications (17)
(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)
ECKERT, HELLMUT. Structural characterization of bioactive glasses by solid state NMR. Journal of Sol-Gel Science and Technology, v. 88, n. 2, p. 263-295, . (13/07793-6, 13/23490-3)
DE OLIVEIRA, JR., MARCOS; UESBECK, TOBIAS; GONCALVES, TASSIA S.; MAGON, CLAUDIO JOSE; PIZANI, PAULO S.; DE CAMARGO, ANDREA S. S.; ECKERT, HELLMUT. Network Structure and Rare-Earth Ion Local Environments in Fluoride Phosphate Photonic Glasses Studied by Solid-State NMR and Electron Paramagnetic Resonance Spectroscopies. Journal of Physical Chemistry C, v. 119, n. 43, p. 24574-24587, . (13/23490-3, 13/07793-6)
DE OLIVEIRA, JR., MARCOS; AITKEN, BRUCE; ECKERT, HELLMUT. Structure of P2O5-SiO2 Pure Network Former Glasses Studied by Solid State NMR Spectroscopy. Journal of Physical Chemistry C, v. 122, n. 34, p. 19807-19815, . (13/23490-3, 13/07793-6)
BENNDORF, CHRISTOPHER; DE OLIVEIRA JUNIOR, MARCOS; BRADTMUELLER, HENRIK; STEGEMANN, FRANK; POETTGEN, RAINER; ECKERT, HELLMUT. Rare-earth solid-state NMR spectroscopy of intermetallic compounds: The case of the Lu-175 isotope. SOLID STATE NUCLEAR MAGNETIC RESONANCE, v. 101, p. 63-67, . (13/23490-3, 13/07793-6)
GALLEANI, GUSTAVO; SANTAGNELI, SILVIA HELENA; MESSADDEQ, YOUNES; DE OLIVEIRA, JR., MARCOS; ECKERT, HELLMUT. Rare-earth doped fluoride phosphate glasses: structural foundations of their luminescence properties. Physical Chemistry Chemical Physics, v. 19, n. 32, p. 21612-21624, . (13/23490-3, 13/07793-6, 15/22828-6)
DE OLIVEIRA, JR., MARCOS; KNITSCH, ROBERT; SAJID, MUHAMMAD; STUTE, ANNIKA; ELMER, LISA-MARIA; KEHR, GERALD; ERKER, GERHARD; MAGON, CLAUDIO J.; JESCHKE, GUNNAR; ECKERT, HELLMUT. Aminoxyl Radicals of B/P Frustrated Lewis Pairs: Refinement of the Spin-Hamiltonian Parameters by Field- and Temperature-Dependent Pulsed EPR Spectroscopy. PLoS One, v. 11, n. 6, . (15/04063-2, 13/23490-3, 13/07793-6)
ZHANG, RUILI; DE OLIVEIRA, MARCOS; WANG, ZAIYANG; FERNANDES, ROGER GOMES; DE CAMARGO, ANDREA S. S.; REN, JINJUN; ZHANG, LONG; ECKERT, HELLMUT. Structural Studies of Fluoroborate Laser Glasses by Solid State NMR and EPR Spectroscopies. Journal of Physical Chemistry C, v. 121, n. 1, p. 741-752, . (13/07793-6, 13/23490-3, 15/04063-2)
DE OLIVEIRA, JR., MARCOS; WIEGAND, THOMAS; ELMER, LISA-MARIA; SAJID, MUHAMMAD; KEHR, GERALD; ERKER, GERHARD; MAGON, CLAUDIO JOSE; ECKERT, HELLMUT. Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs). Journal of Chemical Physics, v. 142, n. 12, . (13/23490-3, 13/07793-6)
DE OLIVEIRA, JR., MARCOS; OLIVEIRA, JANETE SCHULTZ; KUNDU, SWARUP; PEREIRA MACHADO, NORMA MARIA; RODRIGUES, ANA CANDIDA M.; ECKERT, HELLMUT. Network former mixing effects in ion-conducting lithium borotellurite glasses: Structure/property correlations in the system (Li2O)(y)[2(TeO2)(x)(B2O3)(1) (- x)](1-y). Journal of Non-Crystalline Solids, v. 482, p. 14-22, . (13/23490-3)
MUNHOZ, JOAO F. V. L.; SANTAGNELI, SILVIA HELENA; DE OLIVEIRA, JR., MARCOS; MARTINS RODRIGUES, ANA CANDIDA; ECKERT, HELLMUT; NALIN, MARCELO. Glasses in the NaPO3-WO3-NaF ternary system: preparation, physical properties and structural studies. Journal of Non-Crystalline Solids, v. 505, p. 379-389, . (13/23490-3, 13/07793-6, 15/22828-6)
DE OLIVEIRA JR, MARCOS; AMJAD, RAJA JUNAID; DE CAMARGO, ANDREA S. S.; ECKERT, HELLMUT. Network Former Mixing Effects in Heavy Metal Oxide Glasses: Structural Characterization of Lead Zinc Phosphotellurite Glasses Using NMR and EPR Spectroscopies. Journal of Physical Chemistry C, v. 122, n. 41, p. 23698-23711, . (13/07793-6, 15/08434-5, 13/23490-3)
EUSTERWIEMANN, S.; DOERENKAMP, C.; DRESSELHAUS, T.; JANKA, O.; DE OLIVEIRA, JR., M.; DANILIUC, C. G.; ECKERT, H.; NEUGEBAUER, J.; POETTGEN, R.; STUDER, A.. Strong intermolecular antiferromagnetic verdazyl-verdazyl coupling in the solid state. Physical Chemistry Chemical Physics, v. 19, n. 24, p. 15681-15685, . (13/23490-3)
DE OLIVEIRA, JR., MARCOS; GONCALVES, TASSIA S.; FERRARI, CYNTHIA; MAGON, CLAUDIO JOSE; PIZANI, PAULO S.; DE CAMARGO, ANDREA S. S.; ECKERT, HELLMUT. Structure-Property Relations in Fluorophosphate Glasses: An Integrated Spectroscopic Strategy. Journal of Physical Chemistry C, v. 121, n. 5, p. 2968-2986, . (15/04063-2, 13/23490-3, 13/07793-6)
DIERKES, TOBIAS; SEIDEL, STEFAN; BENNDORF, CHRISTOPHER; HELETTA, LUKAS; DE OLIVEIRA JUNIOR, MARCOS; HOLTKAMP, MICHAEL; KARST, UWE; BLOCK, THERESA; JUESTEL, THOMAS; ECKERT, HELLMUT; et al. Mixed europium valence in Eu0.937Ba8[BN2](6) - Structure and spectroscopic behavior. SOLID STATE SCIENCES, v. 70, p. 86-92, . (13/23490-3)
DE VRIES, WILKE; DOERENKAMP, CARSTEN; ZENG, ZHAOYANG; DE OLIVEIRA, JR., MARCOS; NIEHAUS, OLIVER; POETTGEN, RAINER; STUDER, ARMIDO; ECKERT, HELLMUT. Synthesis and characterization of amorphous mesoporous silica using TEMPO-functionalized amphiphilic templates. Journal of Solid State Chemistry, v. 237, p. 93-98, . (13/23490-3, 13/07793-6)
BENNDORF, CHRISTOPHER; DE OLIVEIRA, MARCOS; DOERENKAMP, CARSTEN; HAARMANN, FRANK; FICKENSCHER, THOMAS; KOESTERS, JUTTA; ECKERT, HELLMUT; POETTGEN, RAINER. B-11 and Y-89 solid state MAS NMR spectroscopic investigations of the layered borides YTB4 (T = Mo, W, Re). DALTON TRANSACTIONS, v. 48, n. 3, p. 1118-1128, . (17/06649-0, 13/23490-3)

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