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Metal-Organic Framework-Based Engineered Materials—Fundamentals and Applications
Open AccessArticle

Coordination Polymers Based on a Biphenyl Tetraphosphonate Linker: Synthesis Control and Photoluminescence

1
Department of Chemistry, CICECO—Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
2
QOPNA and LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
3
Department of Physics, CICECO—Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal
4
CQE and Departamento de Engenharia Química Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, no 1, 1049-001 Lisboa, Portugal
*
Author to whom correspondence should be addressed.
These authors contributed equally to this work.
Academic Editor: Alessandro Stroppa
Molecules 2020, 25(8), 1835; https://doi.org/10.3390/molecules25081835
Received: 25 March 2020 / Revised: 9 April 2020 / Accepted: 15 April 2020 / Published: 16 April 2020
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
In this work, we used the rigid tetrapodal organic linker, [1,1′-biphenyl]-3,3′,5,5′-tetrayltetrakis(phosphonic acid) (H8btp), for the preparation of two lanthanide–organic framework families of compounds: layered [Ln7(H5btp)4(H5.5btp)2(H6btp)2(H2O)12]∙23.5H2O∙MeOH [where Ln3+ = Eu3+ (1Eu) and Gd3+ (1Gd)], prepared using microwave-irradiation followed by slow evaporation; 3D [Ln4(H3btp)(H4btp)(H5btp)(H2O)8]∙3H2O [where Ln3+ = Ce3+ (2Ce), Pr3+ (2Pr), and Nd3+ (2Nd)], obtained from conventional hydro(solvo)thermal synthesis. It is shown that in this system, by carefully selecting the synthetic method and the metal centers, one can increase the dimensionality of the materials, also increasing structural robustness (particularly to the release of the various solvent molecules). Compound 1 is composed of 2D layers stacked on top of each other and maintained by weak π–π interactions, with each layer formed by discrete 1D organic cylinders stacked in a typical brick-wall-like fashion, with water molecules occupying the free space in-between cylinders. Compound 2, on the other hand, is a 3D structure with small channels filled with crystallization water molecules. A full solid-state characterization of 1 and 2 is presented (FT-IR spectroscopy, SEM microscopy, thermogravimetric studies, powder X-ray diffraction and thermodiffractometry). The photoluminescence of 1Eu was investigated. View Full-Text
Keywords: metal-organic framework; crystal structure; photoluminescence metal-organic framework; crystal structure; photoluminescence
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MDPI and ACS Style

Firmino, A.D.G.; Mendes, R.F.; Ananias, D.; Barbosa, J.S.; Tomé, J.P.C.; Almeida Paz, F.A. Coordination Polymers Based on a Biphenyl Tetraphosphonate Linker: Synthesis Control and Photoluminescence. Molecules 2020, 25, 1835.

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