Controlling the White‐Light Generation of [(RSn)₄E₆]: Effects of Substituent and Chalcogenide Variation

Abstract

Abstract 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.