Germanium Salts Research Articles

Germanium Halides Serving as Ideal Precursors: Designing a More Effective and Less Toxic Route to High-Optoelectronic-Quality Metal Halide Perovskite Nanocrystals.

The three-precursors approach has proven to be advantageous for obtaining high-quality metal halide perovskite nanocrystals (PNCs). However, the current halide precursors of choice are mainly limited to those highly toxic organohalides, being unfavorable for large-scale and sustainable use. Moreover, most of the resulting PNCs still suffer from low quality in terms of photoluminescence quantum yield (PLQY). Herein we present all-inorganic germanium salts, GeX4 (X = Cl, Br, I), serving as robust and less hazardous alternatives that are capable of ensuring improved material properties for both Pb-based and Pb-free PNCs. Importantly, unlike most of the other inorganic halide sources, the GeX4 compound does not deliver the Ge element into the final compositions, whereas the PLQY and phase stability of the resulting nanocrystals are significantly improved. Theoretical calculations suggest that Ge halide precursors provide favorable conditions in both dielectric environment and thermodynamics, which jointly contribute to the formation of size-confined defect-suppressed nanoparticles.

Stereocontrolled Synthesis of Triols Containing Four Asymmetric Centers: Application of C, O-Chelated Germyl Enolates to a Diastereoselective Aldol Reaction.

The treatment of α,β-unsaturated ketones with divalent germanium salts cleanly generated C, O-chelated germyl enolates. The aldol reactions of the chelated enolates with the aldehydes achieved a high diastereoselectivity in the construction of the five-membered aldol adducts. Furthermore, the subsequent transformation of the Ge-C bond in the aldol adduct enabled the stereocontrolled synthesis of triols bearing four asymmetric centers.

Spectroscopic ellipsometry characterization of spin-coated Ge25S75 chalcogenide thin films

Abstract Spectroscopic ellipsometry study on spin-coated non-toxic Ge25S75 thin films annealed at different temperatures were conducted. Multi sample analysis with two sets of samples spin-coated onto soda-lime glass and onto silicon wafers was utilized. Optical constants (refractive index n and extinction coefficient k) of these films were determined from ellipsometric data recorded over a wide spectral range (0.05–6 eV). Different parametrization of Ge25S75 complex dielectric permittivity which consists of a Tauc-Lorentz or Cody-Lorentz oscillator describing the short wavelength absorption edge, a Lorentz or Gauss oscillators describing phonon absorption or optically active absorption of alkyl ammonium germanium salts in the middle infrared part of spectra is discussed. Using a Mott-Davis model, the decrease in local disorder with increasing annealing temperature is quantified from the short wavelength absorption edge onset. Using the Wemple-DiDomenico single oscillator model for the transparent part of the optical constants spectra, a decrease in the centroid distance of the valence and conduction bands with increasing annealing temperature is shown and increase in intensity of the inter-band optical transition due to annealing temperature occurs. Intensity of absorption near 3000 cm−1 could be used as alternative method to evaluation of quality of prepared films.

Thermochemical study of gaseous salts of oxygen-containing acids: XX. Germanium salts

Reactions of the gas-phase synthesis of germanium vanadate, borate, and molybdate have been studied. Standard enthalpies of formation and atomization of gaseous salts GeV2O6, GeB2O4, and SnMo2O7 have been determined.

Single Crystal Electron Paramagnetic Resonance Spectra of Cs2MnF6 and K2MnF6 Diluted in the Isomorphous Germanium Salts

In this work single crystal electron paramagnetic resonance (EPR) spectra of Cs(2)MnF(6) and K(2)MnF(6) diluted in the similar germanium salts have been interpreted and fitted. The spectra of the cubic cesium salt were recorded with the magnetic field parallel with the 4-fold axis and with the 3-fold axis. The spectrum along the 4-fold axis looks as expected with six groups from the manganese nuclear spin each split into seven lines caused by the nuclear spin from the six fluorine ligands. The spectrum along the 3-fold axis contains considerably more lines. This can be explained by the fact that only the transitions with the M(S) values -1/2<-->1/2 are observed together with the fact that the nuclear Zeeman effect from the six fluorine ligands mixes states and makes forbidden transitions allowed. The spectra of the trigonal potassium salt are recorded along the 3-fold axis and perpendicular to this axis. The sign of the zfs parameter was determined by high frequency EPR spectroscopy at low temperature. The knowledge of this meant that we could determine the sign of the two fluorine hyperfine coupling parameters both in this case and in the cubic case.

Nephrotoxicity and neurotoxicity in humans from organogermanium compounds and germanium dioxide

There is no known biological requirement for germanium (Ge), germanates, or any organogermanium compound. Ge deficiency has not been demonstrated in any animal. The estimated average dietary intake of Ge in humans is 1.5 mg/d. Ge is widely distributed in edible foods, all of which, with few exceptions, contain less than 5 ppm Ge, since higher levels are toxic to most plants. Ingestion of Ge compounds has been shown to produce toxic effects in experimental animals. In recent years inorganic germanium salts and novel organogermanium compounds, such as carboxyethyl germanium sesquioxide (Ge-132) and lactate-citrate-germanate (Ge lactate citrate) have been sold as "nutritional supplements" in some countries for their purported immunomodulatory effects or as health-producing elixirs, resulting in intakes of Ge significantly exceeding the estimated average dietary intake. Since 1982, there have been 18 reported cases of acute renal dysfunction or failure, including two deaths, linked to oral intake of Ge elixirs containing germanium dioxide (GeO2) or Ge-132. In these cases, biopsies show vacuolar degeneration in renal tubular epithelial cells, without proteinuria or hematuria, in the absence of glomerular changes. Serum creatinine levels have been well above 400 mumol/L in such patients. In 17 of 18 cases, accumulated elemental Ge intakes reportedly ranged between 16 to 328 g over a 4-36 mo period, or between 100 to 2000 times the average estimated dietary intake for human. In surviving patients, renal function improved after discontinuation of Ge supplementation. However, in no case was recovery complete. One organogermanium compound, an azaspiran organogermanium compound, 2-aza-8-germanspiro[4,5] decane-2-propamine-8,8-diethyl-N,N-dimethyl dichloride (spirogermanium), has been found to cause both neurotoxicity and pulmonary toxicity in phase I and II studies examining its chemotherapeutic potential as an antitumor drug in the treatment of various malignancies. In cancer patients given the drug spirogermanium, 40% experienced marked, yet transient neurotoxicity. Two patients suffered from pulmonary toxicity. Results of phases I and II human cancer trials for spirogermanium have not been favorable, with the exception of moderate benefits for three types of malignancies. It is recommended that patients exposed to long-term (greater than 3 mo) Ge supplementation at levels well above the estimated daily intake be medically supervised and monitored for potential renal-, pulmonary- or neurotoxicity. Further study regarding the mechanism of Ge-induced nephrotoxicity in human is warranted.

ChemInform Abstract: New Classes of Zerovalent Titanium Carbonyls. First Structural Characterization of a Seven‐Coordinate Titanium Complex Containing Only Unidentate Ligands: Ti(CO)5(SnPh3)22‐.

AbstractConsecutive reduction of the titanium tetrachloride complex (I), reaction with the tin and germanium salts (II) and carbonylation with carbon monoxide (III) yield complexes which are characterized as the tetraethylammonium salts (V).