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Article Dans Une Revue Molecules Année : 2023

Terbium and Europium Chlorocyananilate-Based 2D Coordination Polymers

Mariangela Oggianu
Alexandre Abhervé
Daniela Marongiu
  • Fonction : Auteur
Francesco Quochi
José Ramón Galán-Mascarós
Federica Bertolotti
Norberto Masciocchi
Narcis Avarvari
Maria Laura Mercuri

Résumé

Two-dimensional layered coordination polymers based on the hetero-substituted 3-chloro-6-cyano-2,5-dihydroxybenzoquinone ligands, hereafter ClCNAn2− anilate, and LnIII ions (Tb and Eu) are reported. Compounds 1 and 2, formulated as Ln2(ClCNAn)3(DMSO)6 (LnIII = Tb, 1; Eu, 2), and their related intermediates 1′ and 2′, formulated as Ln2(ClCNAn)3(H2O)x·yH2O (x + y likely = 12, Ln = Tb, 1′; and Eu, 2′), were prepared by a conventional one-pot reaction (the latter) and recrystallized from DMSO solvent (the former). Polyhydrated intermediates 1′ and 2′ show very similar XRPD patterns, while, despite their common stoichiometry, 1 and 2 are not isostructural. Compound 1 consists of a 2D coordination framework of 3,6 topology, where [Tb(DMSO)3]III moieties are bridged by three bis-chelating ClCNAn2− ligands, forming distorted hexagons. Ultrathin nanosheets of 1 were obtained by exfoliation via the liquid-assisted sonication method and characterized by atomic force microscopy, confirming the 2D nature of 1. The crystal structure of 2, still showing the presence of 2D sheets with a “hexagonal” mesh and a common (3,6) connectivity, is based onto flat, non-corrugated slabs. Indeed, at a larger scale, the different “rectangular tiles” show clear roofing in 1, which is totally absent in 2. The magnetic behavior of 1 very likely indicates depopulation of the highest crystal-field levels, as expected for TbIII compounds.

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hal-04456020 , version 1 (13-02-2024)

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Mariangela Oggianu, Alexandre Abhervé, Daniela Marongiu, Francesco Quochi, José Ramón Galán-Mascarós, et al.. Terbium and Europium Chlorocyananilate-Based 2D Coordination Polymers. Molecules, 2023, 28 (18), pp.6453. ⟨10.3390/molecules28186453⟩. ⟨hal-04456020⟩
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