Beschreibung:
<jats:p>Optically active cluster compounds [W<jats:sub>6</jats:sub>Br<jats:sub>8</jats:sub>L<jats:sub>6</jats:sub>]<jats:sup>2–</jats:sup> are prepared from Cs<jats:sub>2</jats:sub>[W<jats:sub>6</jats:sub>Br<jats:sub>14</jats:sub>], which is obtained via reduction of WBr<jats:sub>6</jats:sub> with elemental antimony in the presence of CsBr. Cesium ions and six apical bromide ligands of Cs<jats:sub>2</jats:sub>[W<jats:sub>6</jats:sub>Br<jats:sub>14</jats:sub>] are successively replaced for <jats:italic>n</jats:italic>‐tetrabutyl ammonium (TBA)<jats:sup>+</jats:sup> and ligands (L). Light yellow single‐crystals of (TBA)<jats:sub>2</jats:sub>[W<jats:sub>6</jats:sub>Br<jats:sub>8</jats:sub>L<jats:sub>6</jats:sub>] with L = CF<jats:sub>3</jats:sub>COO and C<jats:sub>7</jats:sub>H<jats:sub>7</jats:sub>SO<jats:sub>3</jats:sub> were isolated from dichloromethane solution and structurally characterized by means of X‐ray single‐crystal diffraction. Photoluminescence studies reveal a wide excitation range within 250 to 500 nm for both compounds and a broad emission centered at <jats:italic>λ</jats:italic><jats:sub>em,max</jats:sub> = 735 nm (L = CF<jats:sub>3</jats:sub>COO) and 730 nm (L = C<jats:sub>7</jats:sub>H<jats:sub>7</jats:sub>SO<jats:sub>3</jats:sub>). Oxygen dependencies of emission intensities are reported.</jats:p>