Syntheses, Structures, Photochemical and Magnetic
Properties of Novel Divalent Cd/Mn Coordination Polymers Based on
a Semirigid Tripodal Carboxylate Ligand
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Abstract
The
reactions of a semirigid tripodal carboxylic ligand, 3,5-bi(4-carboxy-phenoxy)-benzoic
acid (H<sub>3</sub>BCPBA) with Cd(NO<sub>3</sub>)<sub>2</sub>/Mn(NO<sub>3</sub>)<sub>2</sub> afford five novel complexes, {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>·(DMA)<sub>2</sub>·(H<sub>2</sub>O)<sub>5</sub>]·7H<sub>2</sub>O·2DMA}<sub><i>n</i></sub> (<b>1</b>), {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>(L<sup>1</sup>)(H<sub>2</sub>O)<sub>6</sub>]·(L<sup>1</sup>)}<sub><i>n</i></sub> (L<sup>1</sup> = 4-[(E)-4-pyridinylazo]pyridine)
(<b>2</b>), {[Cd<sub>3</sub>(BCPBA)<sub>2</sub>(L<sup>2</sup>)·(H<sub>2</sub>O)<sub>3</sub>(DMF)<sub>2</sub>]·2DMF}<sub><i>n</i></sub> (L<sup>2</sup> = 1,3-bis(4-pyridyl)propane)
(<b>3</b>), {[Mn<sub>3</sub>(BCPBA)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·11H<sub>2</sub>O}<sub><i>n</i></sub> (<b>4</b>), {[Mn<sub>3</sub>(BCPBA)<sub>2</sub>(DMF)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·2DMF·9H<sub>2</sub>O}<sub><i>n</i></sub> (<b>5</b>) in the presence
or absence of an auxiliary ligand. Compound <b>1</b> is a three-dimensional
(3D) structure with 3,4-connected net structure. Compound <b>2</b> possesses 3D networks with two 3D → 3D interpenetration frameworks.
Compound <b>3</b> is a 3D sheet structure with a decorated tfz-d
topology. Compound <b>4</b> is a 3D structure which consists
of a two-dimensional (2D) Mn honeycomb net with six infinite Mn rings
and BCPBA<sup>3–</sup> ligands. Compound <b>5</b> is
also a 3D structure, while its 2D Mn honeycomb net with eight infinite
Mn rings is different from that of compound <b>4</b>. The photochemical
property of <b>1</b>–<b>3</b> is performed in the
solid state at room temperature. Magnetic susceptibility measurements
indicate that compounds <b>4</b> and <b>5</b> exhibit
antiferromagnetic coupling between adjacent Mn(II) ions
