Pyrene Tetraphosphonate-Based Metal-Organic Framework: Structure and Photoluminescence


The synthesis of pyrene-1,3,6,8-tetrayltetrakis(phosphonic acid) (H(8)ptp) and its use in the preparation of a new isotypical family of Metal-Organic Frameworks (MOF) using oxalic acid as secondary linker are reported. This new family, generally formulated as [Ln(2)(H(4)ptp)(ox)(H2O)(6)]center dot 5H(2)O [where Ln(3+)= Ce3+(1Ce), Pr3+(1Pr), Nd3+(1Nd), Sm3+(1Sm), Eu3+(1Eu), Gd3+(1Gd), Tb3+(1Tb) and Dy3+(1Dy)], were prepared under hydrothermal conditions and fully characterized using different techniques. The photoluminescence properties of1Euwere studied, showing emission lifetimes of 0.27 +/- 0.01 ms and 0.33 +/- 0.01 ms at 294 K and 12 K, respectively. This family of materials, based on a fully hydrolysed tetraphosphonate pyrene ligand, constitutes the first example of MOFs obtained using this highly fluorescent organic ligand.



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Firmino, ADG; Mendes, RF; Ananias, D; Figueira, F; Tome, JPC; Rocha, J; Paz, FAA

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This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology/MCTES. Thanks are also due to the University of Aveiro and FCT/MCT for the financial support for the QOPNA research Unit (FCT UID/QUI/00062/2019) and CQE (UIDB/00100/2020) research units through national funds and, where applicable, co-financed by the FEDER, within the PT2020 Partnership Agreement. FCT is also gratefully acknowledged for the Ph.D. grant SFRH/BD/84495/2012 (to ADF), and the Junior Research Position CEECIND/00553/2017 (to RFM) the PhD grant. The research contract of FF (REF-168-89-ARH/2018) is funded by national funds (OE), through FCT, in the scope of the framework contract foreseen in Nos. 4, 5 and 6 of article 23 of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19.

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