Influence of Solvent in Solvothermal Syntheses: Change
of Nuclearity in Mixed Valence Co<sup>II/III</sup> Complexes of a
O‑Donor-rich Schiff Base Ligand
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Abstract
We
have found that a change of solvent in a solvothermal synthetic
method may be a useful tool to generate complexes of various nuclearities
keeping the reactants, synthetic conditions, and stoichiometry the
same. Although the process involves serendipity, the potential of
producing change in nuclearity of discrete molecular complexes by
mere change of solvent ratios provides an additional scope to tune
nuclearity using the same precursors. The above methodology led us
to generate three complexes of different nuclearity bearing the formula
[Co<sup>II</sup>Co<sup>III</sup>(H<sub>2</sub>L)<sub>2</sub>(OAc)]·2CH<sub>3</sub>OH·H<sub>2</sub>O (<b>1</b>), [Co<sup>II</sup><sub>3</sub> Co<sup>III</sup><sub>3</sub>(HL)<sub>2</sub>(H<sub>2</sub>L)<sub>2</sub>(OAc)<sub>2</sub> ]·9CH<sub>3</sub>OH·H<sub>2</sub>O (<b>3</b>), [Co<sup>II</sup><sub>5</sub>Co<sup>III</sup><sub>4</sub>(HL)<sub>4</sub>(H<sub>2</sub>L)<sub>4</sub>(Cl)<sub>2</sub>]·4H<sub>2</sub>O (<b>4</b>) [where, H<sub>4</sub>L = 2-(3,5-di-<i>ter</i>t-butyl-2-hydroxybenzylideneamino)-2-(hydroxymethyl)propane-1,3-diol].
Using the same reactants, stoichiometry, and solvent used to generate <b>3</b> (in solvothermal method) if we reflux on the benchtop we
get the dinuclear complex <b>1</b>, but on addition of 3,5-dimethylpyrazole
a tetranuclear Co<sup>II/III</sup> complex [Co<sup>II</sup><sub>2</sub>Co<sup>III</sup><sub>2</sub>(HL)<sub>2</sub>(OAc)<sub>2</sub>(CH<sub>3</sub>OH)<sub>2</sub>(DMP)<sub>2</sub>]·CH<sub>3</sub>COOH·H<sub>2</sub>O (<b>2</b>) is obtained. All
the complexes were characterized by various spectroscopic and analytical
methods including single crystal X-ray crystallography. The temperature
dependence of magnetic susceptibility of <b>3</b> and <b>4</b> show that the Co<sup>II</sup> centers are weakly coupled
within a single molecule and exhibit both ferro- and antiferromagnetic
interactions. <b>3</b> was found to be active in conversion
of 3,5-di-<i>tert</i>-butylcatechol to 3,5-di-<i>tert</i>-butylbenzoquinone and produces hydrogen peroxide