Description:
<jats:title>Abstract</jats:title><jats:p>In order to gain more information on the white‐light generation by amorphous molecular materials, the influence of metal complex substituents on the photophysical properties of potential white‐light emitters is investigated. Three compounds of the general type [{(R<jats:sub>3</jats:sub>P)<jats:sub>3</jats:sub>MSn}{PhSn}<jats:sub>3</jats:sub>S<jats:sub>6</jats:sub>)], with R/M = Me/Au (<jats:bold>1</jats:bold>), Et/Ag (<jats:bold>4</jats:bold>), and Me/Cu (<jats:bold>5</jats:bold>), are produced by reactions of the organotin sulfide cluster [(PhSn)<jats:sub>4</jats:sub>S<jats:sub>6</jats:sub>] (<jats:bold>A</jats:bold>) with the corresponding coinage metal complexes [M(PR<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>Cl]. Excess of the gold complex in the reaction leads to rearrangement and formation of [Au(PMe<jats:sub>3</jats:sub>)<jats:sub>4</jats:sub>][Au(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>][(PhSnCl)<jats:sub>3</jats:sub>S<jats:sub>4</jats:sub>] (<jats:bold>2</jats:bold>). The use of PMe<jats:sub>3</jats:sub> instead of PEt<jats:sub>3</jats:sub> in the reaction with the silver salt causes decomposition and affords [(Me<jats:sub>3</jats:sub>P)<jats:sub>3</jats:sub>AgSnCl<jats:sub>3</jats:sub>] (<jats:bold>3</jats:bold>). All compounds are structurally characterized, and the necessity of sterically stabilizing PEt<jats:sub>3</jats:sub> groups at the silver complex in <jats:bold>4</jats:bold> are rationalized by density functional theory (DFT) calculations. Measurements of the photophysical properties of <jats:bold>1</jats:bold>, <jats:bold>4</jats:bold>, and <jats:bold>5</jats:bold> show that the introduction of the metallo‐ligands indeed affects the materials properties, and at the same time confirm that the reduction of the molecular symmetry alone is not a sufficient condition for white‐light generation (WLG), which still requires amorphicity of the compound. This is realized for <jats:bold>1</jats:bold> and <jats:bold>4</jats:bold> in situ, while reabsorption processes inhibit WLG in case of the copper compound <jats:bold>5</jats:bold>.</jats:p>