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

Abstract

Adamantane‐type organotin chalcogenide clusters of the general composition [(RT)4S6] (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)4E6] (R=phenyl, cyclopentadienyl, cyclohexyl, benzyl, CH2CH2(C6H4)CO2Et; E=S, Se), were prepared, characterized, and investigated for their nonlinear optical properties. With the exception of crystalline [(BnSn)4S6], 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.

Structure Determination in a New Class of Amorphous Cluster Compounds with Extreme Nonlinear Optical Properties

“…( 4) and are displayed by the lines. Structural data based on DFT calculations 13,14) were used for the computations. They confirm that the molecular structure is well reflected by in the experimental data for the amorphous solids, and that the basic structural motifs of heteroadamantane clusters can basically be confirmed for all of the materials.…”

Amorphous Molecular Materials for Directed Supercontinuum Generation

“…Habitus [a] Optical response Remarks [(StySn) 4 S 6 ] (1) [8] a WLG Sty = styryl [(PhSn) 4 S 6 ] (2) [12] a WLG [(MeSn) 4 S 6 ] (3) [12] a SHG [(NpSn) 4 S 6 ] (4) [12] a SHG Beginning order, π stacking [(BnSn) 4 S 6 ] (5) [10] c SHG [(R 1 Sn) 4 S 6 ] (6) [10] a WLG R 1 = (CH 2 ) 2 À (C 6 H 4 )CO 2 Et [(η 1 -CpSn) 4 S 6 ] (7) [10] a WLG [(CySn) 4 S 6 ] (8) [10] a WLG [(PhSn) 4 Se 6 ] (9) [10] a WLG [(BnSn) 4 Se 6 ] (10) [10] c WLG Melts upon irradiation [(R 1 Sn) 4 Se 6 ] (11) [10] a WLG R 1 = (CH 2 ) 2 À (C 6 H 4 )CO 2 Et [(η 1 -CpSn) 4 Se 6 ] (12) [10] a WLG [(CySn) 4 Se 6 ] (13) [10] a WLG [(PhGe) 4 S 6 ] (14) [12] a WLG [(PhSi) 4 S 6 ] (15) [9] c SHG [(NpSi) 4 S 6 ] (16) [9] c None Decomposition 1,3,5,7-Tetraphenyl-adamantane (17) [13] a WLG Nearly insoluble material [34] c SHG [{(Me 3 P) 3 AuSn}(PhSn) 3 S 6 ] (18) [11] c WLG Amorphization upon laser irradiation [{(Et 3 P) 3 AgSn}(PhSn) 3 S 6 ] (19) [11] c WLG Amorphization upon laser irradiation [{(Me 3 P) 3 CuSn}(PhSn) 3 S 6 ] (20) [11] c None WLG hindered by re-absorption…”

“…Deviations from this behavior in experiments thus arise from structural defects and amorphous Reproduced under terms of the CC-BY license. [10] Copyright 2019, The Authors, Published by Wiley-VCH. Reproduced under terms of the CC-BY license.…”

“…Emission spectra of 5 and 10 after excitation with a 1450 nm laser. e: The larger excitation wavelength was chosen in these experiments to suppress the excitation laser line.Reproduced under terms of the CC-BY license [10]. Copyright 2019, The Authors, Published by Wiley-VCH.…”

Origin of crystallization suppression in a new amorphous molecular white-light-generating material

“…Only one crystalline example exists, namely with benzyl groups as ligands. However, its crystal structure shows no dimer formation and is determined from interactions between the organic ligands, which are arranged regularly in the crystal lattice [16]. The sulfur atoms in the amorphous [(PhSn) 4 S 6 ] solid try to distribute themselves uniformly like a close-meshed net, and it is tempting to identify this as a vibrational network.…”