18-Crown-6 Coordinated Metal Halides with Bright Luminescence and Nonlinear Optical Effects.

The crown-ether coordination compounds ZnX2(18-crown-6), EuX2(18-crown-6) (X: Cl, Br, I), MnI2(18-crown-6), Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) are obtained by ionic-liquid-based synthesis. Whereas MX2(18-crown-6) (M: Zn, Eu) show conventional structural motives, Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) exhibit unusual single MnX4 tetrahedra coordinated to the crown-ether complex. Surprisingly, some compounds show outstanding photoluminescence. Thus, rare Zn2+-based luminescence is observed and unexpectedly efficient for ZnI2(18-crown-6) with a quantum yield of 54%. Unprecedented quantum yields are also observed for Mn3I6(18-crown-6)2, EuBr2(18-crown-6), and EuI2(18-crown-6) with values of 98, 72, and 82%, respectively, which can be rationalized based on the specific structural features. Most remarkable, however, is Mn2I4(18-crown-6). Its specific structural features with finite sensitizer-activator couples result in an extremely strong emission with an outstanding quantum yield of 100%. Consistent with its structural features, moreover, anisotropic angle-dependent emission under polarized light and nonlinear optical (NLO) effects occur, including second-harmonic generation (SHG). The title compounds and their optical properties are characterized by single-crystal structure analysis, X-ray powder diffraction, chemical analysis, density functional theory (DFT) calculations, and advanced spectroscopic methods.

Intensely Photoluminescent Diamidophosphines of the Alkaline-Earth Metals, Aluminum, and Zinc.

The positively charged and weakly polarizable s-block metals commonly do not usually have phosphine ligands in molecular complexes. Herein, we report mono- and dinuclear small diamidophosphine complexes of the alkaline-earth metals Mg, Ca, and Sr, which were prepared from simple precursors and a phosphine-functionalized diamine ligand N,N-bis(2-(diphenyl-phosphino)phenyl)ethane-1,2-diamine (PNHNHP). The alkaline-earth metal based complexes [(PNNP)Mg]2 and [(PNNP)M(thf)3 ] (M=Ca, Sr), exhibit unusual coordination spheres and show bright fluorescence, both in the solid state and in solution. For comparison, the even stronger luminescent Al and Zn complexes [(PNNP)Zn]2 and [(PNNP)AlCl] were prepared. Emission lifetimes in the nanosecond range and high photoluminescence quantum yields up to 93 % are observed at room temperature.

Photodiode-based cutting interruption sensor for near-infrared lasers.

We report on a photodiode-based sensor system to detect cutting interruptions during laser cutting with a fiber laser. An InGaAs diode records the thermal radiation from the process zone with a ring mirror and optical filter arrangement mounted between a collimation unit and a cutting head. The photodiode current is digitalized with a sample rate of 20 kHz and filtered with a Chebyshev Type I filter. From the measured signal during the piercing, a threshold value is calculated. When the diode signal exceeds this threshold during cutting, a cutting interruption is indicated. This method is applied to sensor signals from cutting mild steel, stainless steel, and aluminum, as well as different material thicknesses and also laser flame cutting, showing the possibility to detect cutting interruptions in a broad variety of applications. In a series of 83 incomplete cuts, every cutting interruption is successfully detected (alpha error of 0%), while no cutting interruption is reported in 266 complete cuts (beta error of 0%). With this remarkable high detection rate and low error rate, the possibility to work with different materials and thicknesses in combination with the easy mounting of the sensor unit also to existing cutting machines highlight the enormous potential for this sensor system in industrial applications.

Development of methods for evaluating toxicity to freshwater ecosystems.

This article presents a summary of a collaborative research program involving five European research groups, that was partly funded by the European Commission under its Environmental Research Program. The objective of the program was to develop aquatic toxicity tests that could be used to obtain data for inclusion at Level 2 of the Risk Evaluation Scheme for the Notification of Substances as required by the 7th Amendment to EC Directive 79/831/EEC. Currently only a very limited number of test methods have been described that can be used for this purpose and these are based on an even smaller number of test species. Tests based upon algae (Chlamydomonas reinhardi, Scenedesmus subspicatus, and Euglena gracilis), protozoa (Tetrahymena pyriformis), rotifera (Brachionus calyciflorus), crustacea (Gammarus pulex), and diptera (Chironomus riparius) were developed. The tests encompassed a range of end points and were evaluated against four reference chemicals: lindane, 3, 4-dichloroaniline (DCA), atrazine, and copper. The capacity of the tests to identify concentrations that are chronically toxic in the field was addressed by comparing the effects threshold concentrations determined in the laboratory tests with those determined for similar and/or related species and end points in stream and pond mesocosm studies. The lowest no-observed-effect concentrations (NOEC), EC(x), or LC(x) values obtained for lindane, atrazine, and copper were comparable with the lowest values obtained in the mesocosms. The lowest chronic NOEC determined for DCA using the laboratory tests was approximately 200 times higher than the lowest NOEC in the mesocosms.