| Summary: | We report the synthesis, structural and magnetic characterization of the complete series of lanthanoid-based chloranilato 2D lattices with dimethylsulfoxide (dmso) formulated as: [Ln<sub>2</sub>(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>(dmso)<sub>6</sub>] with Ln = La(<b>1</b>), Ce(<b>2</b>), Pr(<b>3</b>), Nd(<b>4</b>), Sm(<b>5</b>), Eu(<b>6</b>), Gd(<b>7</b>) and Tb(<b>8</b>) or [Ln<sub>2</sub>(C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub>)<sub>3</sub>(dmso)<sub>4</sub>]·2dmso·2H<sub>2</sub>O with Ln = Dy(<b>9</b>), Ho(<b>10</b>), Er(<b>11</b>), Tm(<b>12</b>) and Yb(<b>13</b>); C<sub>6</sub>O<sub>4</sub>Cl<sub>2</sub><sup>2−</sup> = dianion of 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone = chloranilato. Single crystal X-ray analysis shows that the largest Ln(III) ions (La–Tb, <b>1</b>–<b>8</b>) crystallise in the monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> space group (phase I), whereas the smallest ones (Dy–Yb, <b>9</b>–<b>13</b>) crystallise in the triclinic <i>P</i>-1 space group (phase II). Both phases show a (6,3)-2D network with the typical hexagonal honeycomb lattice, although phase I presents important distortions, resulting in rectangular cavities with a brick-wall orientation. The largest ions (phase I) show a coordination number of nine with a capped square antiprismatic geometry in contrast to the smallest ions (phase II) that present a coordination number of eight with a triangular dodecahedral geometry. Magnetic measurements show that all the Ln(III) ions are magnetically well isolated, leading to the presence of a field induced single-ion magnet behaviour in the Er derivative, with an energy barrier of 23(2) K for DC fields of 20, 50 and 100 mT.
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