Beschreibung:
<jats:p>Cluster compounds (TBA)<jats:sub>2</jats:sub>[Mo<jats:sub>6</jats:sub>I<jats:sub>8</jats:sub>(CF<jats:sub>3</jats:sub>SO<jats:sub>3</jats:sub>)<jats:sub>6</jats:sub>], (TBA)<jats:sub>2</jats:sub>[W<jats:sub>6</jats:sub>I<jats:sub>8</jats:sub>(CF<jats:sub>3</jats:sub>SO<jats:sub>3</jats:sub>)<jats:sub>6</jats:sub>], and (TBA)<jats:sub>2</jats:sub>[W<jats:sub>6</jats:sub>Br<jats:sub>8</jats:sub>(CF<jats:sub>3</jats:sub>SO<jats:sub>3</jats:sub>)<jats:sub>6</jats:sub>] are prepared and structurally characterized from single‐crystal X‐ray diffraction data. All compounds show red emission on photoexcitation at 400 nm. However, the phosphorescence of crystalline samples is quenched in the presence of oxygen, depending on the partial pressure of oxygen. The distinct phosphorescence‐quenching behavior of compounds containing trifluoromethanesulfonato (CF<jats:sub>3</jats:sub>SO<jats:sub>3</jats:sub><jats:sup>–</jats:sup>) ligands is compared with corresponding compounds with trifluoroacetato (CF<jats:sub>3</jats:sub>COO<jats:sup>–</jats:sup>) and <jats:italic>p</jats:italic>‐toluolsulfonato (CH<jats:sub>3</jats:sub>C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>SO<jats:sub>3</jats:sub><jats:sup>–</jats:sup>) ligands. By studying these compounds, we investigate the relationship of more‐ or less‐electron‐withdrawing ligands (L) of (TBA)<jats:sub>2</jats:sub>[M<jats:sub>6</jats:sub>X<jats:sub>8</jats:sub>L<jats:sub>6</jats:sub>] halide (X) clusters, their redox potentials (<jats:italic>E</jats:italic><jats:sup>0</jats:sup>), and their phosphorescence‐quenching behavior under variable oxygen partial pressures.</jats:p>