preprints.org > chemistry and materials science > electronic, optical and magnetic materials > doi: 10.20944/preprints202308.0394.v1

Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Version 1 : Received: 3 August 2023 / Approved: 3 August 2023 / Online: 4 August 2023 (08:34:17 CEST)

Two-dimensional layered coordination polymers based on the hetero-substituted 3-chloro-6-cyano-2,5-dihydroxybenzoquinone ligand, hereafter ClCNAn2- anilate, and LnIII ions (Tb and Eu) are reported. Compounds 1, 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. 1 consists of a 2D coordination framework of 3,6 topology, where [Tb(DMSO)3]3+ moieties are bridged by three bis-chelating ClCNAn2- ligands, forming distorted hexagons. Ultrathin nanosheets of 1 were obtained by exfoliation, via 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 “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 a 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.

Lanthanides; 2D Coordination Polymers; Nanosheets; Anilates

Chemistry and Materials Science, Electronic, Optical and Magnetic Materials

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