Abstract
Incorporating transition metal ions into Lindqvist polyoxovanadate-alkoxide (POV-alkoxide) clusters has been shown to be an effective method for tuning the electronic properties of these molecular assemblies. Herein, we report the synthesis of a gallium-functionalized POV-alkoxide cluster, extending the family of heterometal-functionalized clusters to a metalloid ion. Complex [V5O6(OCH3)12GaCl] was characterized by infrared and electronic absorption spectroscopies and cyclic voltammetry, revealing the retention of the extensive delocalization upon installation of the 3d10 ion. The new reaction conditions developed for [V5O6(OCH3)12GaCl] were shown to successfully generate the iron analogue, [V5O6(OCH3)12FeCl], from a ferric salt precursor. However, attempts at installing other group 13 ions, e.g. InIII, instead produced the cyclic hexavanadate cluster, [Bu4N][V6O6(OCH3)12Cl].
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