Alteration of Nonlinear Refraction by Mixing Clusters [WOS₃Cu₃I(py)₅] and [MoOS₃Cu₃I(py)₅]

Abstract

A new cluster compound [WOS 3 Cu 3 I(py) 5 ] (I) was synthesized by substitution reactions of (Et 4 N) 3 [WOS 3 -Cu 3 I 4 ] with pyridine and structurally determined by X-ray diffraction. It crystallizes in monoclinic, space group C2/c (No. 15), a ) 24.341(1), b ) 10.020(4), c ) 26.64(1) Å, V ) 6424(3) Å 3 , and Z ) 8. The cluster has a nest-shaped skeleton. The nonlinear optical properties of both I and [MoOS 3 Cu 3 I(py) 5 ] (II) in acetonitrile solutions were measured using a Z-scan technique with 7-ns and 532-nm laser pulses. Compound I possesses a self-focusing property (n 2 ) 1.6 × 10 -9 cm 2 W -1 M -1 ), while compound II exhibits a self-defocusing property (n 2 ) -1.3 × 10 -10 cm 2 W -1 M -1 ). Both compounds show reverse saturable absorption (R 2 ) 1.5 × 10 -4 and 2.5 × 10 -5 cm W -1 M -1 for compounds I and II, respectively). We demonstrate that the nonlinear refraction of a mixture containing the two compounds can be altered from self-focusing, through a state where self-lensing disappears, to self-defocusing by varying the ratio of the two compounds.

The First Assembly of a Nest-Shaped Heterothiometallic Cluster and a Polyoxometalate Anion − Synthesis, Characterization, and Strong Third-Order Nonlinear Optical Response

“…To the best of our knowledge, the nest‐shaped clusters always adopt the configuration of a neutral skeleton, e.g. [MOS 3 Cu 3 I(py) 5 ],11b or an anionic skeleton, e.g. [Bu 4 N] 2 [MOS 3 Cu 3 BrCl 2 ]11a or [PPh 4 ] 2 [MOS 3 (CuCl) 3 ]18 (M = Mo, W).…”

Nonlinear Optical Materials for the Smart Filtering of Optical Radiation

“…References to clusters come along with the definition of their skeletons shape. They usually are linear, butterfly, cubane-like, , nest, half-open cubic-cage, pentanuclear planar “open”, ,, hexagonal-prism, twin-nest, supra-cage, and polymeric clusters. − All of these structures have been shown to possess NLO properties resulting in strong OL effects. Adjustment of the NLO properties on heterothiometallic clusters can be realized through the manipulation of the structural units, peripheral ligands, and skeleton elements. , Furthermore, incorporation of heavy metal atoms brings in more sublevels into the energy scheme, thus permitting a larger number of allowed electronic transitions.…”

Synthesis, structural characterization and third-order non-linear optical property of new three-dimensional metal-organic framework (M=Ni, Co)

“…Of course, there exist several isostructural compounds containing different NLO properties. For instance, cluster [MoOS 3 Cu 3 I(py) 5 ] (py = pyridine) possesses self-defocusing property, while cluster [WOS 3 Cu 3 I(py) 5 ] exhibits self-focusing property [21]. With regard to the title compounds, the peak/valley patterns of the normalized transmittance curves mean a negative sign for the refractive non-linearity, which indicate both possess characteristic self-defocusing behavior (n 2 < 0).…”