White-Light Generation Upon In-Situ Amorphization of Single Crystals of [{(Me3P)3AuSn}(PhSn)3S6] and [{(Et3P)3AgSn}(PhSn)3S6]

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 [{(R3P)(3)MSn}{PhSn}(3)S-6)], with R/M = Me/Au (1), Et/Ag (4), and Me/Cu (5), are produced by reactions of the organotin sulfide cluster [(PhSn)(4)S-6] (A) with the corresponding coinage metal complexes [M(PR3)(3)Cl]. Excess of the gold complex in the reaction leads to rearrangement and formation of [Au(PMe3)(4)][Au(PMe3)(2)][(PhSnCl)(3)S-4] (2). The use of PMe3 instead of PEt3 in the reaction with the silver salt causes decomposition and affords [(Me3P)(3)AgSnCl3] (3). All compounds are structurally characterized, and the necessity of sterically stabilizing PEt3 groups at the silver complex in 4 are rationalized by density functional theory (DFT) calculations. Measurements of the photophysical properties of 1, 4, and 5 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 1 and 4 in situ, while reabsorption processes inhibit WLG in case of the copper compound 5.