Local Cluster Distortions in Amorphous Organotin Sulfide Compounds and Their Influence on the Nonlinear Optical Properties

Abstract

The local structure of four amorphous organotin sulfide compounds is investigated by X‐ray absorption spectroscopy. These compounds exhibit a nonlinear optical (NLO) response upon irradiation with a continuous‐wave near‐infrared laser. Their basic structural motif is a hetero‐adamantane cluster with different organic substituent, but depending on the morphology of the compound and the choice of the organic substituent, the nature of the NLO response changes to either a second harmonic generation or the generation of a supercontinuum, potentially appearing as white light. The structural results provide an experimental evidence that the nature of the NLO properties is tied to distortions occurring at the cluster core, with almost ideal clusters in compounds that show second harmonic generation, and strongly distorted clusters in the case of compounds that generate a supercontinuum. These distortions may enable a closer proximity of the cluster cores, altering the intermolecular order, and thereby influencing the NLO response.

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[655][656][657][658] It showed up thereby however, that the control of the morphology is complex and a simple assignment amorphous/WLG, crystalline/SHG is so far still ambiguous. It was however found from EXAFS experiments [659] that the molecular structure of adamantane-like cluster materials showing SHG (586 and 591) was close to that found from quantum chemical calculations, [660] while those showing WLG (587 and 602) did considerably deviate from these structures. Please do not adjust margins Please do not adjust margins…”

Enhancement of birefringence and refractive index dispersion optimization from iodates to fluorooxoiodates

“…Nonlinear optical (NLO) materials have become an important part of laser science and technology, enabling a tunable output of lasers through frequency conversion techniques. [1][2][3][4][5][6][7][8][9][10][11][12] Over the last few decades, high performance NLO materials have been continuously researched and rapidly developed, [13][14][15][16][17][18][19][20][21][22][23] and numerous NLO materials including borates, [24][25][26][27][28][29] carbonates, 30 phosphates, 31 sulfates, 32,33 iodates, 34,35 and nitrates 36 have been reported. The introduction of F atoms into the matrix to produce new NLO materials with excellent optical properties was found to be an effective strategy 37 due to the greater electronegativity of the F atoms.…”