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High-throughput investigation of new rare earth-doped bismuth-based metal-organic frameworks (MOFs)

Grant number: 16/03640-9
Support type:Scholarships abroad - Research Internship - Doctorate (Direct)
Effective date (Start): December 29, 2016
Effective date (End): November 28, 2017
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
Principal Investigator:Hermi Felinto de Brito
Grantee:Cesar dos Santos Cunha
Supervisor abroad: Norbert Stock
Home Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
Local de pesquisa : Kiel University, Germany  
Associated to the scholarship:13/07521-6 - Preparation of supramolecular - MOF systems containing rare earth ions and their photoluminescent properties investigation, BP.DD


The development of organic light emitting diodes (OLEDs) attracts interest due to their potential application in electroluminescent devices for full-color flat panel displays and television screens. Materials that present the possibility of color tuning can be applied for instance to produce different light emitting materials, including white emitters. However, obtaining efficient hosts to produce Rare Earth (RE) codoped compounds that allow to reduce concentration quenching effects as well as to improve quantum efficiency and tune the emission color are critical challenges in photonic science. Trivalent bismuth is nontoxic, non-carcinogenic and has an ionic radius, charge and coordination sphere similar to trivalent RE ions. Hence, Bi3+ based metal-organic frameworks (MOFs) are very advantageous hosts for RE-doped materials. Moreover, the so-called high-throughput (HT) synthesis methods are faster and more efficient than conventional approaches applied so far to discover new compounds and optimize synthesis procedures. Therefore, this method will be used here to obtain new MOFs containing the p-tetrakis-carboxymethylcalix-4-arene ligand and the Bi3+ ions. The new hosts materials will be doped with the RE ions, such as Eu3+, Tb3+, Sm3+, Gd3+, Tm3+, Dy3+ and mixtures thereof. The photoluminescent properties will be studied based on the excitation and emission spectra to characterize the energy transfer process between the excited states of the MOF host lattice to the emitters levels of the RE ions as well as the energy transfer between the dopant ions themselves. The lifetime of the emitting levels of the RE ions, the color CIE diagram (x,y), the experimental intensity parameters, the spontaneous emission coefficients and emission quantum efficiency will be determined. In addition, the influence of the crystal field on the transitions 5D0 -> 7FJ (J = 0-6) of Eu3+ ions will be applied to confirm the crystallographic position of the dopants. (AU)

Scientific publications
(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)
CÉSAR S. CUNHA; OSCAR L. MALTA; HUAYNA TERRASCHKE; HERMI F. BRITO. Photoluminescent Investigation of the Doping Site of Eu3+-Doped [Zn3(BTC)2·12H2O] Metal-Organic Framework Prepared by Microwave-Assisted Hydrothermal Synthesis. Journal of the Brazilian Chemical Society, v. 31, n. 11, p. 2409-2420, Nov. 2020. Web of Science Citations: 0.
CUNHA, C. S.; KOEPPEN, M.; TERRASCHKE, H.; FRIEDRICHS, G.; MALTA, O. L.; STOCK, N.; BRITO, H. F. Luminescence tuning and single-phase white light emitters based on rare earth ions doped into a bismuth coordination network. JOURNAL OF MATERIALS CHEMISTRY C, v. 6, n. 46, p. 12668-12678, DEC 14 2018. Web of Science Citations: 3.
RHAUDERWIEK, TIMO; CUNHA, CESAR DOS SANTOS; TERRASCHKE, HUAYNA; STOCK, NORBERT. Bismuth Coordination Polymers with 2,4,6-Pyridine Tricarboxylic Acid: High-Throughput Investigations, Crystal Structures and Luminescence Properties. European Journal of Inorganic Chemistry, n. 27, p. 3232-3240, JUL 23 2018. Web of Science Citations: 0.

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