Terbium and Europium Chlorocyananilate-Based 2D Coordination Polymers

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 center dot 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.