Structure, Electrochemistry, and Magnetism of the Iron(III)-Substituted Keggin Dimer, [Fe<sub>6</sub>(OH)<sub>3</sub>(<i>A-</i>α<i>-</i>GeW<sub>9</sub>O<sub>34</sub>(OH)<sub>3</sub>)<sub>2</sub>]<sup>11-</sup>

The iron(III)-substituted tungstogermanate [Fe<sub>6</sub>(OH)<sub>3</sub>(<i>A</i><i>-</i>α<i>-</i>GeW<sub>9</sub>O<sub>34</sub>(OH)<sub>3</sub>)<sub>2</sub>]<sup>11-</sup> (<b>1</b>) has been synthesized and characterized by IR, elemental analysis, SQUID magnetometry, electron paramagnetic resonance (EPR), and electrochemistry. Single-crystal X-ray analysis was carried out on Cs<sub>4</sub>Na<sub>7</sub>[Fe<sub>6</sub>(OH)<sub>3</sub>(<i>A</i><i>-</i>α<i>-</i>GeW<sub>9</sub>O<sub>34</sub>(OH)<sub>3</sub>)<sub>2</sub>]·30H<sub>2</sub>O, which crystallizes in the monoclinic system, space group <i>C</i><sub>2/<i>m</i></sub>, with <i>a</i> = 36.981(4) Å, <i>b</i> = 16.5759(15) Å, <i>c</i> = 16.0678(15) Å, β = 95.311(3)°, and <i>Z</i> = 4. Polyanion <b>1</b> consists of two (<i>A-</i>α<i>-</i>GeW<sub>9</sub>O<sub>34</sub>) Keggin moieties linked via six Fe<sup>3+</sup> ions, leading to a double-sandwich structure. The equivalent iron centers represent a trigonal prismatic Fe<sub>6</sub> fragment, resulting in virtual <i>D</i><sub>3</sub><i><sub>h</sub></i> symmetry for <b>1</b>. Electrochemistry studies revealed that <b>1</b> is stable in solution from pH 3 to at least pH 7. In pH = 3 media the reduction of the six Fe<sup>3+</sup> centers was featured by a single voltammetric wave for most supporting electrolytes used. In that case, whatever the scan rate from 1000 mV·s<sup>-1</sup> down to 2 mV·s<sup>-1</sup>, no splitting of the single Fe-wave of <b>1</b> was observed. The acetate medium induced a partial splitting of the wave, and this separation is enhanced with increasing pH. Remarkable efficiency of <b>1</b> in the electrocatalytic reduction of nitrite, nitric oxide, and nitrate is demonstrated. Magnetic susceptibility (χ) measurements indicate a diamagnetic (<i>S</i><sub>T</sub> = 0) ground state, with an average <i>J</i> = −12 cm<sup>-1</sup> and <i>g</i> = 2.00. EPR studies confirm that the ground state is indeed diamagnetic, since the EPR signal intensity steadily decreases without any line broadening as the temperature is lowered and becomes unobservable below about 50 K. The signal is a single broad peak at all frequencies (90−370 GHz), ascribed to the thermally accessible excited states. Its <i>g</i><sub>iso</sub> is 1.992 51, as expected for a high-spin Fe<sup>3+</sup>-containing species, and supports the χ data analysis.