RESUMEN
The usability of the alkali niobates with their ferroelectric and photorefractive properties could be expanded if the development of synthesis methods would allow to obtain small, preferably monodispersed, crystals in the sub-µm to nanometer regime. Of all the possible synthesis methods, the most reliable is currently hydrothermal synthesis to generate small crystallite sizes of these materials. Although the products of sodium niobate are polydisperse and partially agglomerated, they show a significant SHG signal that is unexpectedly comparable to that of potassium niobate. A view on the hydrothermal synthesis of sodium niobate reveals that the incorporation of cations in the crystalline lattice of the niobium educt plays a part in the formation of the product. The occurrence of distinct different phases, as in the case of potassium niobate, is not observed. Instead, it is shown that a clear assignment of the crystalline phase cannot be made here. This indicates that crystallization of the alkali niobates in hydrothermal synthesis depends on the stoichiometry, the niobium starting material and the cation used.
RESUMEN
The complex trans-[RuNO(NH3)4F]SiF6 was synthesized in quantitative yield and the structure was characterized by X-ray diffraction and spectroscopic methods. The complex crystallizes in the non-centrosymmetric space group Pn. Hirshfeld surface analysis revealed that the dominant intermolecular interactions are of types H...F and F...O, which are likely to be responsible for the packing of the molecules in a non-centrosymmetric structure. Irradiation with blue light leads to the formation of Ru-ON (metastable state MS1) and Ru-η2-(NO) (metastable state MS2) bond isomers, as shown by IR and UV-Vis spectroscopy. The structural features of the MS1 isomer were elucidated by photocrystallography. The complex exhibits exceptionally good thermal stability of the metastable state MS1, such that it can be populated by light at 290-300â K, which is important for potential applications. The second harmonic (SH) emission can be generated by femtosecond-pulsed irradiation of the complex. The generated SH is rather efficient and stable under long-term exposure. Finally, since both metastable states and harmonic generation can be generated at room temperature, an attempt to drive the SH response by photoisomerization of the nitrosyl ligand was made and is discussed.
RESUMEN
The structural and nonlinear optical properties of a new anilinium hybrid crystal of chemical formula (C6H7NCl+·NO3-)3 have been investigated. The crystal structure was determined from single-crystal X-ray diffraction measurements performed at a temperature of 100â K which show that the compound crystallizes in a noncentrosymmetric space group (Pna21). The structural analysis was coupled with Hirshfeld surface analysis to evaluate the contribution of the different intermolecular interactions to the formation of supramolecular assemblies in the solid state that exhibit nonlinear optical features. This analysis reveals that the studied compound is characterized by a three-dimensional network of hydrogen bonds and the main contributions are provided by the O...H, C...H, H...H and Cl...H interactions, which alone represent â¼85% of the total contributions to the Hirshfeld surfaces. It is noteworthy that the halogen...H contributions are quite comparable with those of the H...H contacts. The nonlinear optical properties were investigated by nonlinear diffuse femtosecond-pulse reflectometry and the obtained results were compared with those of the reference material LiNbO3. The hybrid crystals exhibit notable second (SHG) and third (THG) harmonic generation which confirms its polarity is generated by the different intermolecular interactions. These measurements also highlight that the THG signal of the new anilinium compound normalized to its SHG counterpart is more pronounced than for LiNbO3.
RESUMEN
Nanocrystals of alkaline niobates are currently being discussed for various applications because of their diverse and remarkable properties. Although the growth of bulk niobate crystals is well established, little is known about respective nanocrystals and the optical properties of niobates below 100 nm. A systematic view of the hydrothermal synthesis of potassium niobate with respect to the precursor species reveals the sensitive dependence of the resulting crystalline phases and sizes on the educt modifications. With a variation of stoichiometry of the procedure, the product modification and crystallite size can be changed. By means of second harmonic generation, nanocrystalline potassium niobate offers the possibility for use as an optical marker in high resolution nonlinear microscopy. Redispersed particles show a significant second harmonic generation signal throughout the visible spectral range.