Combined Experimental/Theoretical Study on the Luminescent Properties of Homoleptic/Heteroleptic Erbium(III) Anilate-Based 2D Coordination Polymers

Abstract

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Metal-Organic Framework vs. Coordination Polymer—Influence of the Lanthanide on the Nature of the Heteroleptic Anilate/Terephtalate 3D Network

“…The absorption onset of ClCNAn 2− is clearly visible below 650 nm in all compounds. At longer wavelengths, the spectra are dominated by Yb(III) and Er(III) absorption transitions (979 nm for Yb(III), 1510, 971 and 790 nm for Er(III)) [44,45]. On the other hand, absorption transitions associated to Eu(III) are not visible due to the overlap with those of ClCNAn 2− organic linker.…”

“…The purity of the polycrystalline samples was confirmed by FT-IR (Figure S1) and powder X-ray diffraction (Figures S2-S4). It should be noted that in our previous studies [44,45], one-pot room-temperature synthesis or layering techniques were used using the same precursor reagents and resulted in 2D coordination polymers. It thus highlights the influence of solvothermal conditions on the crystallization of 3D structures.…”

“…On the other hand, absorption transitions associated to Eu(III) are not visible due to the overlap with those of ClCNAn 2− organic linker. The band at ~1450 nm in 1 and 2 was assigned to water absorption (this vibration is a combination of symmetrical and antisymmetrical stretchings of the coordinated water molecule) [45,48]. Although the three crystal structures share many features such as the metal to ligands stoichiometry (Ln/ClCNAn 2− /F4BDC 2− ratio of 2/2/1) and the coordination mode of the ligands, the resulting 3D networks present very different topologies.…”

“…As part of our research endeavor on anilate Ln-CPs, we applied herein the multiple linkers strategy, hereafter called heteroleptic strategy, in order to afford 3D Ln-CPs based on the anilate ligands. We thus selected the 3-chloro-6-cyano-2,5-dihydroxy-1,4-benzoquinone (chlorocyananilate, ClCNAn 2− ) and 2,3,5,6-tetrafluoroterephtalate (F 4 BDC 2− , Scheme 1) [42,43] bridging ligands since the use of these two linkers already allowed some of us to obtain heteroleptic 2D Ln-CPs [44,45]. In this work, we have been able to crystallize in a highly reproducible manner, under solvothermal conditions, the 3D compounds of formula…”

Glycols in the Synthesis of Zinc-Anilato Coordination Polymers

“…It changes the polymer structure and affects the physicochemical properties of the resulting derivative. For example, intensive research has begun on the properties of heteroleptic derivatives containing simultaneously two types of ligands in the MOF: anilate and dicarboxylate [27,32,33]. The recent works [34,35] demonstrated the use of polyatomic alcohols as anionic ligands in the synthesis of heteroleptic zinc MOFs.…”