Solvent-Induced Assembly of Octacyanometalates-Based
Coordination Polymers with Unique <i>afm</i>1 Topology and
Magnetic Properties
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Abstract
Aqueous solution was introduced into
the self-assembly of water-insoluble
(Bu<sub>3</sub>NH)<sub>3</sub>[M(CN)<sub>8</sub>] (M = W, Mo) and
Mn(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O to afford two,
three-dimensional (3D) coordination polymers (CPs), {[μ<sub>8</sub>-M<sup>V</sup>(CN)<sub>8</sub>Mn<sup>II</sup><sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>(CH<sub>3</sub>OH)][NO<sub>3</sub>]}<sub><i>n</i></sub> (M = W <b>1</b>, Mo <b>2</b>), while
polymer {[μ<sub>4</sub>-W<sup>V</sup>(CN)<sub>8</sub>Mn<sup>II</sup><sub>2</sub>(DMF)<sub>8</sub>](ClO<sub>4</sub>)}<sub><i>n</i></sub> (DMF = <i>N</i>,<i>N</i>-dimethylformamide)
(<b>3</b>) was crystallized from the reaction of (Bu<sub>3</sub>NH)<sub>3</sub>[W(CN)<sub>8</sub>] and Mn(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O in DMF. All three CPs <b>1</b>, <b>2</b>, and <b>3</b> have been well-characterized by elemental
analysis, infrared spectra, single-crystal X-ray diffraction, as well
as thermogravimetric analysis. The single-crystal X-ray structural
analysis shows that both CPs <b>1</b> and <b>2</b> crystallize
in the monoclinic crystal system with space group of <i>C</i>2/<i>c</i> and possess the infinite 3D framework in an
unprecedented <i>afm</i>1 topology geometry, which is an
unreported 4-nodal 4,4,8,8-coordinated net with point symbol {4<sup>11</sup>.6<sup>12</sup>.8<sup>5</sup>}{4<sup>17</sup>.6<sup>10</sup>.8}{4<sup>5</sup>.6}<sub>4</sub>. Polymer <b>3</b> crystallizes
in the space group of <i>P</i>4<sub>2</sub>/<i>m</i> as a 3D supermolecule structure, which is constructed by one-dimensional
(1D) cationic {[μ<sub>4</sub>-W<sup>V</sup>(CN)<sub>8</sub>Mn<sup>II</sup><sub>2</sub>(DMF)<sub>8</sub>]<sup>+</sup>}<sub><i>n</i></sub> chains linked via the hydrogen bonds. Magnetic susceptibility
measurements in the temperature range of 2–300 K reveal that
CPs <b>1</b> and <b>2</b> exhibit the similar typical
antiferromagnetic properties, while CP <b>3</b> shows the ferromagnetic
property