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Inorganics, Volume 9, Issue 12 (December 2021) – 6 articles

Cover Story (view full-size image): Multidentate tripodal ligands have supported numerous landmark examples of small molecule activation chemistry by uranium complexes over the last 25 years, but in comparison, the f-block chemistry of hexadentate N-donor ligands is immature. Here, we report the synthesis and characterization of a series of lanthanum and uranium complexes containing hexadentate ligands that bind through three amine and three anilide donor atoms. We find that variation of the substituents on the anilide rings provides minor differences in complex solubilities, coordination spheres, and dynamic magnetic properties. Given the importance of the size and shape of apical pockets in small molecule activation processes, we posit that flexible hexadentate N-donor ligand complexes may provide complementary reactivity profiles to those containing related tripodal ligands.View this paper
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Communication
Tripodal Oxazolidine-N-Oxyl Diradical Complexes of Dy3+ and Eu3+
Inorganics 2021, 9(12), 91; https://doi.org/10.3390/inorganics9120091 - 20 Dec 2021
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Abstract
Two diradical complexes of the formula [LnRad2(CF3SO3)3] c (Ln(III) = Dy, Eu, Rad = 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl) were obtained in air conditions. These are the first examples of diradical compounds of lanthanides and oxazolidine nitroxide. The complexes [...] Read more.
Two diradical complexes of the formula [LnRad2(CF3SO3)3] c (Ln(III) = Dy, Eu, Rad = 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl) were obtained in air conditions. These are the first examples of diradical compounds of lanthanides and oxazolidine nitroxide. The complexes were characterized crystallographically and magnetically. Single crystal XRD analysis revealed that their coordination sphere is composed of three monodentate triflates and two tripodal Rad, which coordinate the central atom in a tridentate manner via two N atoms of the pyridine groups and the O atom of a nitroxide group. The LnO5N4 polyhedron represents a spherical capped square antiprism with point symmetry close to C4v. The data of static magnetic measurements are compatible with the presence of two paramagnetic ligands in the coordination sphere of the metal. Full article
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Article
Breakdown Properties of Cables with Different Inorganic, Insulating Nanomaterials
Inorganics 2021, 9(12), 90; https://doi.org/10.3390/inorganics9120090 - 20 Dec 2021
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Abstract
The insulation performance of cable insulating materials can be optimised via matrix modification. Typically, low-density polyethylene (LDPE) is used as the matrix, and a certain proportion of nanoparticles are added to this matrix. To explore the effects of nanoparticles with different forms on [...] Read more.
The insulation performance of cable insulating materials can be optimised via matrix modification. Typically, low-density polyethylene (LDPE) is used as the matrix, and a certain proportion of nanoparticles are added to this matrix. To explore the effects of nanoparticles with different forms on the structural interface and crystal morphology of the material, nano-MMT and nano-ZnO were added to LDPE, and comparative experiments were carried out. Based on microscopic test results, material insulation performance changes before and after optimisation were observed. Then, simulation cable models with different insulating materials were developed. Based on the simulated electrical measurements, the thermal breakdown performance of the different insulating materials was tested. According to infrared stereo vision detection results, anomalous temperature points in the cables can be located accurately. Finally, based on macroscopic test results, we verified whether the inorganic, insulating nanomaterials meet the requirements for high-voltage transmission. Full article
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Article
Sol-Gel Combustion Synthesis, Crystal Structure and Luminescence of Cr3+ and Mn4+ Ions in Nanocrystalline SrAl4O7
Inorganics 2021, 9(12), 89; https://doi.org/10.3390/inorganics9120089 - 16 Dec 2021
Viewed by 395
Abstract
A series of strontium dialuminate SrAl4O7 nanopowders with the grossite-type structure doped with chromium and manganese ions were synthesized by the combined sol–gel solution combustion method with use of two different strontium salts. The Cr3+ and Mn4+ ions [...] Read more.
A series of strontium dialuminate SrAl4O7 nanopowders with the grossite-type structure doped with chromium and manganese ions were synthesized by the combined sol–gel solution combustion method with use of two different strontium salts. The Cr3+ and Mn4+ ions concentrations were varied from 0.05 to 5 at.%. Evolution of phase composition, crystal structure, and microstructural parameters of the nanocrystalline materials depending on the synthesis conditions, temperature of thermal treatment, and dopant content were investigated by the X-ray powder diffraction and the scanning electron microscopy techniques. Photoluminescent properties of SrAl4O7 nanophosphors activated with Cr3+ and Mn4+ ions were studied at room temperature. The samples exhibit typical photoluminescence in the deep-red spectral region, corresponding to d-d transitions in Cr3+ or Mn4+ ions. The intensity of this deep-red emission is dependent on the dopant concentration and annealing temperature. Features of the formation of octahedral surroundings around Cr3+ or Mn4+ ions are discussed. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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Article
Europium-Doped Y2O3-Coated Diatomite Nanomaterials: Hydrothermal Synthesis, Characterization, Optical Study with Enhanced Photocatalytic Performance
Inorganics 2021, 9(12), 88; https://doi.org/10.3390/inorganics9120088 - 14 Dec 2021
Viewed by 483
Abstract
Eu-doped Y2O3 coated diatomite nanostructures with variable Eu3+ contents were synthesized by a facile hydrothermal technique. The products were characterized by means of energy dispersive X-ray photoelectron spectroscopy (EDX), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Brunauer–Emmett–Teller (BET), [...] Read more.
Eu-doped Y2O3 coated diatomite nanostructures with variable Eu3+ contents were synthesized by a facile hydrothermal technique. The products were characterized by means of energy dispersive X-ray photoelectron spectroscopy (EDX), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Brunauer–Emmett–Teller (BET), UV-vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy techniques. As claimed by PXRD, the particles were crystallized excellently and attributed to the cubic phase of Y2O3. The influence of substitution of Eu3+ ions into Y2O3 lattice caused a redshift in the absorbance and a decrease in the bandgap of as-prepared coated compounds. The pore volume and BET specific surface area of Eu-doped Y2O3-coated diatomite is greater than uncoated biosilica. The sonophotocata-lytic activities of as-synthesized specimens were evaluated for the degradation of Reactive Blue 19. The effect of various specifications such as ultrasonic power, catalyst amount, and primary dye concentration was explored. Full article
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Article
PbS1−xSex[email protected]/P3HT Nanocomposites with Tunable Photoelectric Conversion Performance
Inorganics 2021, 9(12), 87; https://doi.org/10.3390/inorganics9120087 - 10 Dec 2021
Viewed by 551
Abstract
The photoelectric performance of quantum dots (QDs)-based nanocomposites is closely related to the optical properties of QDs, which play a critical role in the optical absorption and separation/transfer of charge carriers. Herein, we report a nanocomposite composed of light absorber PbS1−xSe [...] Read more.
The photoelectric performance of quantum dots (QDs)-based nanocomposites is closely related to the optical properties of QDs, which play a critical role in the optical absorption and separation/transfer of charge carriers. Herein, we report a nanocomposite composed of light absorber PbS1−xSex quantum dots (QDs), electron-conducting multiwalled carbon nanotubes (MWCNTs) and hole-conducting poly-3-hexylthiophene (P3HT) with tunable photoelectric conversion performance. In addition to using the quantization effect, we proposed solid-solution PbS1−xSex QDs (x = 0, 0.25, 0.5, 0.75, 1) for band gap engineering. In particular, we successfully synthesized relatively small (~5.3 nm) and uniform QDs via the hot-injection method by using PbCl2, S/Se powder and environmentally friendly oleylamine (OLA) as the precursors and/or solvent. By increasing the content of Se, the band gap of PbS1−xSex QDs decreased along with the decrease in the conduction band and valence band edges. The suitable energy level alignment enabled the efficient transfer of photoinduced charge carriers, and hence a much higher photoelectric conversion performance of the PbS1−xSex[email protected]/P3HT nanocomposites than the individual QDs, P3HT, and binary PbS1−xSex[email protected], as well as the best performance, was achieved over PbS0.75Se0.25[email protected]/P3HT. Full article
(This article belongs to the Section Inorganic Materials)
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Article
Functionalized Tris(anilido)triazacyclononanes as Hexadentate Ligands for the Encapsulation of U(III), U(IV) and La(III) Cations
Inorganics 2021, 9(12), 86; https://doi.org/10.3390/inorganics9120086 - 28 Nov 2021
Viewed by 663
Abstract
Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we [...] Read more.
Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we functionalized the previously reported tris-anilide ligand {tacn(SiMe2NPh)3} (tacn = 1,3,7-triazacyclononane) to incorporate substituted aromatic rings, with the aim of modifying f-element complex solubility and ligand steric effects. We report the synthesis of two proligands, {tacn(SiMe2NHAr)3} (Ar = C6H3Me2-3,5 or C6H4Me-4), and their respective group 1 transfer agents—{tacn(SiMe2NKAr)3}, M(III) complexes [M{tacn(SiMe2NAr)3}] for M = La and U, and U(IV) complexes [M{tacn(SiMe2NAr)3}(Cl)]. These compounds were characterized by multinuclear NMR and FTIR spectroscopy and elemental analysis. The paramagnetic uranium complexes were also characterized by solid state magnetic measurements and UV/Vis/NIR spectroscopy. U(III) complexes were additionally studied by EPR spectroscopy. The solid state structures of all f-block complexes were authenticated by single-crystal X-ray diffraction (XRD), together with a minor byproduct [U{tacn(SiMe2NC6H4Me-4)3}(I)]. Comparisons of the characterization data of our f-element complexes with similar literature examples containing the {tacn(SiMe2NPh)3} ligand set showed minor changes in physicochemical properties resulting from the different aromatic ring substitution patterns we investigated. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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