Controlling the White‐Light Generation of [(RSn)(4)E(6)]: Effects of Substituent and Chalcogenide Variation

Adamantane‐type organotin chalcogenide clusters of the general composition [(RT)(4)S(6)] (R=aromatic substituent, T=Si, Ge, Sn) have extreme non‐linear optical properties that lead to highly directional white‐light generation (WLG) upon irradiation with an IR laser diode. However, the mechanism is not yet understood. Now, a series of compounds [(RSn)(4)E(6)] (R=phenyl, cyclopentadienyl, cyclohexyl, benzyl, CH(2)CH(2)(C(6)H(4))CO(2)Et; E=S, Se), were prepared, characterized, and investigated for their nonlinear optical properties. With the exception of crystalline [(BnSn)(4)S(6)], all these compounds exhibit WLG with similar emission spectra; slight blue‐shifts are observed by introduction of cyclopentadienyl substituents, while the introduction of Se in the inorganic core can provoke a red‐shift. These investigations disprove the initial assumption of an aromatic substituent being a necessary precondition; the precondition seems to be the presence of (cyclic) substituents providing enough electron density.