Template-Assisted Synthesis
of Co,Mn-MOFs with Magnetic
Properties Based on Pyridinedicarboxylic Acid
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Abstract
To investigate the influence
of organic molecules with reactive functional groups as templates
on the structures of the resulting MOFs, four novel complexes based
on the pyridyl carboxylic acid ligand 5-(pyridin-4-yl)isophthalic
acid (H<sub>2</sub>pyip), namely, [Mn<sub>3</sub>(pyip)<sub>2</sub>(HCOO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub><i>n</i></sub> (<b>1</b>), {[Co(pyip)(H<sub>2</sub>O)]·H<sub>2</sub>O}<sub><i>n</i></sub> (<b>2</b>), {[Mn<sub>2</sub>(pyip)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]·5H<sub>2</sub>O}<sub><i>n</i></sub> (<b>3</b>), and [Co(pyip)(EtOH)(H<sub>2</sub>O)]<sub><i>n</i></sub> (<b>4</b>), have been
synthesized under solvothermal conditions. In the presence of 4,4′-bipyridyl
as the template, 3D coordination framework <b>1</b> with the
Schläfli symbol of (4·6·7) (4<sup>2</sup>·5·6<sup>5</sup>·7<sup>3</sup>·8<sup>2</sup>·9·11) was
obtained. Using cyanoacetic acid as the template, we obtained 2D double-layered
structure <b>2</b> with the Schläfli symbol of (4<sup>3</sup>) (4<sup>6</sup>·6<sup>6</sup>·8<sup>3</sup>). <b>3</b> and <b>4</b> are prepared in the absence of a templating
agent. <b>3</b> features an infinite 2D network with a 1D water
chain penetrating the 1D channel and further results in a 3D supramolecule
through hydrogen-bond interactions. <b>4</b> contains two independent
2D networks that are further connected to a 2D double-layered supramolecular
framework by hydrogen bonds. The template-assisted method is a potential
approach for obtaining specific intriguing complexes that might be
difficult to access by routine synthetic methods. Magnetic investigations
revealed that both <b>1</b> and <b>2</b> exhibit weak
antiferromagnetic interactions mediated by pyip<sup>2–</sup>
