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Inorganics
Volume 10
Issue 12
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Inorganics, Volume 10, Issue 12 (December 2022) – 49 articles

Cover Story (view full-size image): In nature, Zr minerals are always accompanied by their less abundant geochemical twin element Hf. The otherwise reoccurring ratio of about 37:1 Zr:Hf shows a striking deviance within certain fluoride-rich ores, which show an about 20 times enriched Hf content. This accumulation is presumably driven by the higher affinity of Hf toward fluoride. Our calculations on bulk Zr/HfO2 and Zr/HfF4 confirm this trend. While all studied oxo/fluoro and oxo-fluoro crystals show higher cohesive energies for the respective Hf species, the difference to Zr is indeed most pronounced for fluorides. This suggests that the phenomenon of fluoride-driven Hf enrichment can be related to the electronic properties of the systems. View this paper
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9 pages, 1154 KiB  
Article
Synthesis and Crystal Structure of the Zintl Phases Na2CaCdSb2, Na2SrCdSb2 and Na2EuCdSb2
by Bayram Saparov and Svilen Bobev
Inorganics 2022, 10(12), 265; https://doi.org/10.3390/inorganics10120265 - 18 Dec 2022
Cited by 2 | Viewed by 1312
Abstract
This work details the synthesis and the crystal structures of the quaternary Zintl phases Na2CaCdSb2, Na2SrCdSb2 and Na2EuCdSb2. They are isostructural and their noncentrosymmetric structure is with the space group Pmc2 [...] Read more.
This work details the synthesis and the crystal structures of the quaternary Zintl phases Na2CaCdSb2, Na2SrCdSb2 and Na2EuCdSb2. They are isostructural and their noncentrosymmetric structure is with the space group Pmc21 (Pearson code oP12). All structural work is carried out via single-crystal X-ray diffraction methods. The structure features [CdSb2]4– layers of corner-shared CdSb4 tetrahedra, which are stacked along the b-crystallographic axis and are separated by cations. The results from the structure refinements suggest that in addition to full cation ordering, which is typical for this structure, there also exists a possibility for an accommodation of a small degree of cation disorder. Full article
(This article belongs to the Special Issue Advances of Thermoelectric Materials)
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14 pages, 2691 KiB  
Article
Hydrothermal Synthesized CoS2 as Efficient Co-Catalyst to Improve the Interfacial Charge Transfer Efficiency in BiVO4
by Yangqin Gao, Guoqing Yang, Zhijie Tian, Hongying Zhu, Lianzheng Ma, Xuli Li, Ning Li and Lei Ge
Inorganics 2022, 10(12), 264; https://doi.org/10.3390/inorganics10120264 - 18 Dec 2022
Viewed by 1415
Abstract
The bare surface of BiVO4 photoanode usually suffers from extremely low interfacial charge transfer efficiency which leads to a significantly suppressed photoelectrochemical water splitting performance. Various strategies, including surface modification and the loading of co-catalysts, facilitate the interface charge transfer process in [...] Read more.
The bare surface of BiVO4 photoanode usually suffers from extremely low interfacial charge transfer efficiency which leads to a significantly suppressed photoelectrochemical water splitting performance. Various strategies, including surface modification and the loading of co-catalysts, facilitate the interface charge transfer process in BiVO4. In this study, we demonstrate that CoS2 synthesized from the hydrothermal method can be used as a high-efficient co-catalyst to sufficiently improve the interface charge transfer efficiency in BiVO4. The photoelectrochemical water splitting performance of BiVO4 was significantly improved after CoS2 surface modification. The BiVO4/CoS2 photoanode achieved an excellent photocurrent density of 5.2 mA/cm2 at 1.23 V versus RHE under AM 1.5 G illumination, corresponding to a 3.7 times enhancement in photocurrent compared with bare BiVO4. The onset potential of the BiVO4/CoS2 photoanode was also negatively shifted by 210 mV. The followed systematic combined optical and electrochemical characterization results reveal that the interfacial charge transfer efficiency of BiVO4 was largely improved from less than 20% to more than 70% due tor CoS2 surface modification. The further surface carrier dynamics study performed using an intensity modulated photocurrent spectroscopy displayed a 6–10 times suppression in surface recombination rate constants for CoS2 modified BiVO4, which suggests that the key reason for the improved interfacial charge transfer efficiency possibly originates from the passivated surface states due to the coating of CoS2. Full article
(This article belongs to the Special Issue Photoelectrodes for Water Splitting)
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15 pages, 2585 KiB  
Article
Yttrium and Lithium Complexes with Diamidophosphane Ligand Bearing 2,1,3-Benzothiazolyl Substituent: Polydentate Complexation and Reversible NH–PH Tautomery
by Radmir M. Khisamov, Taisiya S. Sukhikh, Sergey N. Konchenko and Nikolay A. Pushkarevsky
Inorganics 2022, 10(12), 263; https://doi.org/10.3390/inorganics10120263 - 17 Dec 2022
Cited by 1 | Viewed by 1467
Abstract
Deprotonation of a bis(amino)phosphane H2L = PhP(HNBtd)2 bearing a heterocyclic Btd = 2,1,3-benzothiadiazol-4-yl substituents at nitrogen atoms by silylamides LiNTms2 and Y(NTms2)3 (Tms = trimethylsilylamide) results in lithium and yttrium complexes with the deprotonated HL– [...] Read more.
Deprotonation of a bis(amino)phosphane H2L = PhP(HNBtd)2 bearing a heterocyclic Btd = 2,1,3-benzothiadiazol-4-yl substituents at nitrogen atoms by silylamides LiNTms2 and Y(NTms2)3 (Tms = trimethylsilylamide) results in lithium and yttrium complexes with the deprotonated HL– and L2– forms as κ2-N and κ4-N chelating ligands. A binuclear complex [LiHL]2 was crystallized from Et2O, and was shown to reversibly dissociate in thf (tetrahydrofuran) with the NH(soln)–PH(crystal) tautomeric shift; the compound [Li2L] was spectroscopically characterized. Yttrium readily forms stable bis-ligand complexes [YL2]– and [YL(HL)]. In the latter, the H atom in HL resides on phosphorus; the coordination sphere remains accessible to another ligands, and it was crystallized as [{YL(HL)}2(µ-dioxane)] species (YN8O coordination). In the former complex, the coordination sphere was saturated (YN8) by closer bound ligands; it was crystallized as a salt with [Li(thf)4]+. The monoligand complex could not be cleanly obtained in a 1:1 reaction of H2L and Y(NTms2)3, and was only crystallographically characterized as a dimer [YL(NTms)2]2. Partial oxidation of the central P atom with the formation of phosphine-oxide ligands PhP(O)(NBtd)2– was observed. They co-crystallize in the same position as non-oxidized ligands in [YL2]– and [YL(NTms2)]2 species and participate in bonding between two units in the latter. TD-DFT calculations reveal that main transitions in the visible region of electronic spectra correspond to the charge transfer bands mostly associated with the orbitals located on Btd fragments. Full article
(This article belongs to the Section Coordination Chemistry)
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10 pages, 2507 KiB  
Article
Two-Dimensional and Three-Dimensional Coordination Polymers Based on Ln(III) and 2,5-Diiodoterephthalates: Structures and Luminescent Behavior
by Alexander S. Zaguzin, Mikhail A. Bondarenko, Pavel A. Abramov, Marianna I. Rakhmanova, Maxim N. Sokolov, Vladimir P. Fedin and Sergey A. Adonin
Inorganics 2022, 10(12), 262; https://doi.org/10.3390/inorganics10120262 - 16 Dec 2022
Cited by 2 | Viewed by 1462
Abstract
Five new coordination polymers based on Ln3+ and 2,5-diiodoterephthalates (2,5-I-bdc)— {[La2(2,5-I-bdc)3(DMF)4]}·2DMF (1) and {[Ln2(2,5-I-bdc)3(DMF)4]} (Ln = La (2), Nd (3), Sm (4) [...] Read more.
Five new coordination polymers based on Ln3+ and 2,5-diiodoterephthalates (2,5-I-bdc)— {[La2(2,5-I-bdc)3(DMF)4]}·2DMF (1) and {[Ln2(2,5-I-bdc)3(DMF)4]} (Ln = La (2), Nd (3), Sm (4) and Eu (5))—were prepared and characterized by single crystal and powder X-ray diffractometry. Luminescent behavior was examined (the highest quantum yield is 4.5%); thermal stability was examined using thermogravimetric analysis. Full article
(This article belongs to the Special Issue Light Emitting Metal Complexes)
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15 pages, 4850 KiB  
Article
Polymeric Copper(II) Complexes with a Newly Synthesized Biphenyldicarboxylic Acid Schiff Base Ligand—Synthesis, Structural and Thermal Characterization
by Milica G. Bogdanović, Nikola D. Radnović, Berta Barta Holló, Mirjana M. Radanović, Branko B. Kordić, Vidak N. Raičević, Ljiljana S. Vojinović-Ješić and Marko V. Rodić
Inorganics 2022, 10(12), 261; https://doi.org/10.3390/inorganics10120261 - 16 Dec 2022
Viewed by 1492
Abstract
The newly synthesized biphenyldicarboxylic acid Schiff base and its complexes with Cu(II) were synthesized, and their spectroscopic and structural analysis was performed. The reaction of the ligand and copper(II) acetate in different solvents resulted in the formation of two solvatomorphic complexes, one with [...] Read more.
The newly synthesized biphenyldicarboxylic acid Schiff base and its complexes with Cu(II) were synthesized, and their spectroscopic and structural analysis was performed. The reaction of the ligand and copper(II) acetate in different solvents resulted in the formation of two solvatomorphic complexes, one with MeOH, and the other with DMF molecules, in the crystal lattice. The differences in the results of the thermal analysis could be explained by the different polarities of the solvents present. SC-XRD analysis revealed that the ligand is coordinated as a dianion, in a pentadentate manner, through two phenoxide oxygen atoms, two azomethine nitrogen atoms, and with the oxygen atom of one carboxylate functioning as a bridge that connects the monomeric units. The coordination polyhedron was described with several parameters obtained from different methods of calculation. The presence of different solvents in the crystal structure results in differences in the H-bond networks, and an overall different crystal packing of the structural units in the obtained complexes. Full article
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23 pages, 7299 KiB  
Article
Green Synthesis of Fe3O4 Nanoparticles and Its Applications in Wastewater Treatment
by Shahnaz Bassim, Alyaa K. Mageed, Adnan A. AbdulRazak and Hasan Sh. Majdi
Inorganics 2022, 10(12), 260; https://doi.org/10.3390/inorganics10120260 - 15 Dec 2022
Cited by 9 | Viewed by 2693
Abstract
In this paper, the extract of Citrus aurantium (CA) was used as a green approach for the preparation of Fe3O4 nanoparticles. The green Fe3O4 (Fe3O4/CA) was characterized by X-ray diffraction (XRD), scanning electron [...] Read more.
In this paper, the extract of Citrus aurantium (CA) was used as a green approach for the preparation of Fe3O4 nanoparticles. The green Fe3O4 (Fe3O4/CA) was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy analysis (EDX), Fourier-transform infrared (FTIR) spectroscopy, Brunauer–Emmett–Teller (BET) surface area measurement, and vibrating sample magnetometry (VSM). The synthesized Fe3O4/CA was used to remove methylene blue (MB) dye from an aqueous solution. A four-factor central composite design (CCD), combined with response surface modeling (RSM), was used to maximize the MB dye removal. The four independent variables, which were initial dye concentration (10–50 mg/L), solution pH (3–9), adsorbent dose (ranging from 200–1000 mg/L), and contact time (30–90 min), were used as inputs to the model of the perecentage dye removal. The results yielded by an analysis of variance (ANOVA) confirmed the high significance of the regression model. The predicted values of the MB dye removal were in agreement with the corresponding experimental values. Optimized conditions for the maximum MB dye removal (93.14%) by Fe3O4/CA were the initial dye concentration (10.02 mg/L), pH (8.98), adsorbent mass (997.99 mg/L), and contact time (43.71 min). The validity of the quadratic model was examined, and good agreement was found between the experimental and predicted values. Our findings demonstrated that green Fe3O4NPs is a good adsorbent for MB removal. Full article
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17 pages, 12355 KiB  
Article
Stability of Hydroxo/Oxo/Fluoro Zirconates vs. Hafniates—A DFT Study
by Jennifer Anders, Fabian Göritz, Anselm Loges, Timm John and Beate Paulus
Inorganics 2022, 10(12), 259; https://doi.org/10.3390/inorganics10120259 - 13 Dec 2022
Cited by 1 | Viewed by 1181
Abstract
We performed density functional theory (DFT) calculations on binary and ternary oxo/fluoro crystals of the geochemical twin pair zirconium and hafnium to evaluate and compare their stabilities. This is the first DFT study on bulk ZrF4 or HfF4, as well [...] Read more.
We performed density functional theory (DFT) calculations on binary and ternary oxo/fluoro crystals of the geochemical twin pair zirconium and hafnium to evaluate and compare their stabilities. This is the first DFT study on bulk ZrF4 or HfF4, as well as on a hypothetical ZrOF2 or HfOF2 bulk crystal. For α-MO2, β-MF4 and MOF2, we have found significantly higher cohesive energies for the respective hafnium species. This suggests a considerable gap in affinity toward fluorine and oxygen between the twin pair in the solid state. In agreement with experimental findings, this gap is slightly more pronounced for fluorine. This study is also the first to evaluate the theoretical, endothermic mono-hydroxylation of the respective fluorides or oxyfluorides to model the difference in affinity toward fluoride versus hydroxide. For these, we could also find a slight energetic preference for the hafnium compound. Full article
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13 pages, 2925 KiB  
Article
Structural Characteristics, Stability, and Electronic Properties of 001 Surface with Point Defects of Zinc Stannate: A First-Principle Study
by Jun Li, Meilin Zhu, Rou Feng, Yingjie Yuan, Zewei Fu, Liangliang Meng, Yingwu Wang, Ying Zhou, Hui Zhang and Hongcun Bai
Inorganics 2022, 10(12), 258; https://doi.org/10.3390/inorganics10120258 - 13 Dec 2022
Viewed by 1099
Abstract
This work presents first-principles calculations on the surface and defect impact upon zinc stannate (ZS) materials with perovskite bulk structures. The structure and electronic properties of both a perfect 001 surface and surfaces with a point defect of ZS were investigated by means [...] Read more.
This work presents first-principles calculations on the surface and defect impact upon zinc stannate (ZS) materials with perovskite bulk structures. The structure and electronic properties of both a perfect 001 surface and surfaces with a point defect of ZS were investigated by means of density functional theory calculations. The cohesive energies of a perfect 001 surface and those with O, Sn, or Zn defects were decreased compared with that of bulk ZS. Oxygen defects on the 001 surface of ZS formed more easily than others based on the obtained cohesive energy and defect formation energy. The electronic properties close to the Fermi levels of bulk ZS materials were mainly controlled by the O 2p and Sn 5s orbitals. The formation of vacancy on the 001 surface of ZS changed the band structure and band gap compared with that of the bulk. The modulation mechanism was explored by means of structure transformation, band structure, and density of states analysis. Full article
(This article belongs to the Topic Theoretical, Quantum and Computational Chemistry)
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15 pages, 4440 KiB  
Article
Peppermint-Mediated Green Synthesis of Nano ZrO2 and Its Adsorptive Removal of Cobalt from Water
by Ibrahem Mohamed Abouzeid Hasan, Hanan Salah El-Din and Ahmed A. AbdElRaady
Inorganics 2022, 10(12), 257; https://doi.org/10.3390/inorganics10120257 - 12 Dec 2022
Cited by 3 | Viewed by 1850
Abstract
Zirconium oxide nanoparticles (ZrO2NPs) were green synthesized for the first time using an aqueous peppermint extract as a precipitating and capping agent. Addition of the extract to Zr4+ solution was followed by calcination of the resulting precipitate at 570 and [...] Read more.
Zirconium oxide nanoparticles (ZrO2NPs) were green synthesized for the first time using an aqueous peppermint extract as a precipitating and capping agent. Addition of the extract to Zr4+ solution was followed by calcination of the resulting precipitate at 570 and 700 °C to form ZrO2NPs570 and ZrO2NPs700, respectively. These oxides were characterized using X-ray diffraction, transmission electron microscopy, and BET surface area analysis, and used as adsorbents for cobalt ions (Co2+) in water. The effects of pH, initial Co2+ concentration, ZrO2NPs mass, and contact time on adsorption efficiency were studied. Characterization results showed formation of cubic ZrO2 with average crystallite sizes (XRD data) of 6.27 and 7.26 nm for ZrO2NPs570 and ZrO2NPs700, respectively. TEM images of the two oxides exhibited nearly spherical nanoparticles and BET surface area measurements indicated the formation of mesoporous oxides having surface areas of 94.8 and 62.4 m2/g, respectively. The results of the adsorption study confirmed that the synthesized ZrO2NPs can be efficiently used for the adsorption of Co2+ from water. The uptake of Co2+ from the treated solution is favored at pH values higher than its point of zero charge (6.0). In addition, the adsorption of Co2+ by ZrO2 follows a pseudo-second order kinetics (R2 = 1.0) and can be explained by the Langmuir adsorption isotherm (R2 = 0.973). Full article
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15 pages, 3404 KiB  
Article
Efficient and Rapid Removal of Pb(II) and Cu(II) Heavy Metals from Aqueous Solutions by MgO Nanorods
by Monira G. Ghoniem, Mohamed Ali Ben Aissa, Fatima Adam Mohamed Ali and Mohamed Khairy
Inorganics 2022, 10(12), 256; https://doi.org/10.3390/inorganics10120256 - 11 Dec 2022
Cited by 3 | Viewed by 1544
Abstract
In this study, the adsorption capability of MgO nanorods for the quick and effective elimination of Cu(II) and Pb(II) heavy metals from wastewater was examined. The MgO nanorods were produced via simple coprecipitation process. Various characterization techniques were used to investigate the morphological [...] Read more.
In this study, the adsorption capability of MgO nanorods for the quick and effective elimination of Cu(II) and Pb(II) heavy metals from wastewater was examined. The MgO nanorods were produced via simple coprecipitation process. Various characterization techniques were used to investigate the morphological and chemical properties of the as-prepared nanomaterial. Moreover, the influences of initial heavy-metal ion concentration, pH, and contact time were investigated to evaluate the removal efficiency of the nanomaterials. The adsorption process followed pseudo-second order and Langmuir adsorption isotherm models, according to kinetics and isotherm investigations, respectively. MgO nanoparticles exhibited a high adsorption capacity for Cu(II) (234.34 mg/g) and Pb(II) (221.26 mg/g). The existence of interfering ions in the aqueous solution leads to a decrease in the adsorption capacity. Surface complexation was determined as the key contributor to the adsorption of Cu(II) and Pb(II) heavy-metal ions onto MgO nanorods. Notably, regeneration experiments demonstrate the potential applicability of MgO nanorods for the elimination of Pb(II) and Cu(II) from aqueous solution. Full article
(This article belongs to the Section Inorganic Materials)
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9 pages, 911 KiB  
Communication
Generalized Peukert Equation with Due Account of Temperature for Estimating the Remaining Capacity of Nickel–Metal Hydride Batteries
by Nataliya N. Yazvinskaya
Inorganics 2022, 10(12), 255; https://doi.org/10.3390/inorganics10120255 - 10 Dec 2022
Viewed by 1200
Abstract
In this paper, it is experimentally proven that the generalized Peukert equation C(i,T) = Cm(T)/(1 + (i/i0(T))n(T)) is applicable to nickel–metal hydride [...] Read more.
In this paper, it is experimentally proven that the generalized Peukert equation C(i,T) = Cm(T)/(1 + (i/i0(T))n(T)) is applicable to nickel–metal hydride batteries at any discharge currents, while the classical Peukert equation can be used only in a limited range of the discharge currents (approximately from 0.3 Cn to 3 Cn). In addition, the classical Peikert equation does not take into account the influence of the temperature of a battery on its released capacity. It is also proven that for the nickel–metal hydride batteries, the generalized Peukert equation heavily depends on battery temperature (via the parameters Cm(T), i0(T) and n(T)). The temperature dependencies of the parameters of the generalized Peukert equation and their physical meaning are also established. The obtained generalized Peukert equation, which considers the batteries’ temperature, can be used at any discharge current and temperature of the batteries. Full article
(This article belongs to the Special Issue Beyond Lithium-Ion Battery Technology)
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21 pages, 4731 KiB  
Article
3–(2–Pyridyl)pyrazole Based Luminescent 1D-Coordination Polymers and Polymorphic Complexes of Various Lanthanide Chlorides Including Orange-Emitting Cerium(III)
by Heba Youssef, Alexander E. Sedykh, Jonathan Becker, Ilya V. Taydakov and Klaus Müller-Buschbaum
Inorganics 2022, 10(12), 254; https://doi.org/10.3390/inorganics10120254 - 10 Dec 2022
Cited by 3 | Viewed by 1530
Abstract
A series of 18 lanthanide-containing 1D-coordination polymers 1∞[Ln2(2–PyPzH)4Cl6], Ln = La, Nd, Sm, dinuclear polymorphic complexes α–, β–[Ln2(2–PyPzH)4Cl6], Ln = Sm, Eu, Gd, α–[Tb2(2–PyPzH)4Cl6 [...] Read more.
A series of 18 lanthanide-containing 1D-coordination polymers 1∞[Ln2(2–PyPzH)4Cl6], Ln = La, Nd, Sm, dinuclear polymorphic complexes α–, β–[Ln2(2–PyPzH)4Cl6], Ln = Sm, Eu, Gd, α–[Tb2(2–PyPzH)4Cl6], and [Gd2(2–PyPzH)3(2–PyPz)Cl5], mononuclear complexes [Ce(2–PyPzH)3Cl3], [Ln(2–PyPzH)2Cl3], Ln = Tb, Dy, Ho, and Er, and salt-like complexes [Gd3(2–PyPzH)8Cl8]Cl and [PyH][Tb(2–PyPzH)2Cl4] were obtained from the reaction of the respective lanthanide chloride with the 3–(2–pyridyl)pyrazole (2–PyPzH) ligand at different temperatures. An antenna effect through ligand-to-metal energy transfer was observed for several products, leading to the highest luminescence efficiency displayed by a quantum yield of 92% in [Tb(2–PyPzH)2Cl3]. The Ce3+ ion in the complex [Ce(2–PyPzH)3Cl3] exhibits a bright and orange 5d-based broadband emission with a maximum at around 600 nm, marking an example of a strong reduction of the 5d-excited states of Ce(III). The absorption spectroscopy shows ion-specific 4f–4f transitions, which can be assigned to Nd3+, Sm3+, Eu3+, Dy3+, Ho3+, and Er3+ in a wide spectral range from UV–VIS to the NIR region. Full article
(This article belongs to the Special Issue Metal Complexes with N-donor Ligands)
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9 pages, 2573 KiB  
Article
A One-Dimensional Cu(I) Coordination Polymer with Optical Sensing of Oxygen and Temperature
by Wan-Tao Chen, Chen-Hui Li, Wan-Qing Zhou, Jing-Tao Huang, Jia-Wen Ye and Ling Chen
Inorganics 2022, 10(12), 253; https://doi.org/10.3390/inorganics10120253 - 10 Dec 2022
Cited by 3 | Viewed by 1261
Abstract
Due to their tight structures, it is usually difficult for one-dimensional (1D) coordination polymers (CPs) to form permanent pores unless 2D and 3D topologies are formed via supramolecular interactions, so studies in the field of oxygen sensing on 1D CPs are rarely reported. [...] Read more.
Due to their tight structures, it is usually difficult for one-dimensional (1D) coordination polymers (CPs) to form permanent pores unless 2D and 3D topologies are formed via supramolecular interactions, so studies in the field of oxygen sensing on 1D CPs are rarely reported. Here, we report a 1D Cu(I) cluster-based CP with dual sensing characteristics for temperature and oxygen. Even if the porosity is only 6.6%, the quenching rate of this CP reaches 98.4% with 1 bar O2 at room temperature. Its luminescence intensity exhibits a unique thermal “quenching, then activating” behavior during monotonic variations in temperature. Full article
(This article belongs to the Special Issue Multifunctional MOF Composite for Biomedical Sensing)
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26 pages, 7365 KiB  
Article
[Hexaamminecobalt(III)] Dichloride Permanganate—Structural Features and Heat-Induced Transformations into (CoII,MnII)(CoIII,MnIII)2O4 Spinels
by Laura Bereczki, Vladimir M. Petruševski, Fernanda Paiva Franguelli, Kende Attila Béres, Attila Farkas, Berta Barta Holló, Zsuzsanna Czégény, Imre Miklós Szilágyi and László Kótai
Inorganics 2022, 10(12), 252; https://doi.org/10.3390/inorganics10120252 - 09 Dec 2022
Cited by 5 | Viewed by 1866
Abstract
We synthesized and characterized (IR, Raman, UV, SXRD) hexaamminecobalt(III) dichloride permanganate, [Co(NH3)6]Cl2(MnO4) (compound 1) as the precursor of Co–Mn–spinel composites with atomic ratios of Co:Mn = 1:1 and 1:3. The 3D−hydrogen bond network includes [...] Read more.
We synthesized and characterized (IR, Raman, UV, SXRD) hexaamminecobalt(III) dichloride permanganate, [Co(NH3)6]Cl2(MnO4) (compound 1) as the precursor of Co–Mn–spinel composites with atomic ratios of Co:Mn = 1:1 and 1:3. The 3D−hydrogen bond network includes N–HO–Mn and N–HCl interactions responsible for solid-phase redox reactions between the permanganate anions and ammonia ligands. The temperature-limited thermal decomposition of compound 1 under the temperature of boiling toluene (110 ∘C) resulted in the formation of (NH4)4Co2Mn6O12. which contains a todorokite-like manganese oxide network (MnII4MnIII2O1210−). The heat treatment products of compounds 1 and [Co(NH3)5Cl](MnO4)2 (2) synthesized previously at 500 ∘C were a cubic and a tetragonal spinel with Co1.5Mn1.5O4 and CoMn2O4 composition, respectively. The heating of the decomposition product of compounds 1 and 2 that formed under refluxing toluene (a mixture with an atomic ratio of Co:Mn = 1:1 and 1:2) and after aqueous leaching ((NH4)4Co2Mn6O12, 1:3 Co:Mn atomic ratio in both cases) at 500 ∘C resulted in tetragonal Co0.75Mn2.25O4 spinels. The Co1.5Mn1.5O4 prepared from compound 1 at 500 ∘C during the solid-phase decomposition catalyzes the degradation of Congo red with UV light. The decomposition rate of the dye was found to be nine times faster than in the presence of the tetragonal CoMn2O4 spinel prepared in the solid-phase decomposition of compound 2. The todorokite-like intermediate prepared from compound 1 under N2 at 115 ∘C resulted in a 54 times faster degradation of Congo red, which is a great deal faster than the same todorokite-like phase that formed from compound 2 under N2. Full article
(This article belongs to the Section Coordination Chemistry)
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24 pages, 4019 KiB  
Article
Structural Study of Model Rhodium(I) Carbonylation Catalysts Activated by Indole-2-/Indoline-2-Carboxylate Bidentate Ligands and Kinetics of Iodomethane Oxidative Addition
by Mohammed A. E. Elmakki, Orbett Teboho Alexander, Gertruida J. S. Venter, Johan Andries Venter and Andreas Roodt
Inorganics 2022, 10(12), 251; https://doi.org/10.3390/inorganics10120251 - 08 Dec 2022
Cited by 4 | Viewed by 1315
Abstract
The rigid-backbone bidentate ligands Indoline-2-carboxylic acid (IndoliH) and Indole-2-carboxylic acid (IndolH) were evaluated for rhodium(I). IndoliH formed [Rh(Indoli)(CO)(PPh3)] (A2), while IndolH yielded the novel dinuclear [Rh1(Indol’)(CO)(PPh3)Rh2(CO)(PPh3)2] (B2) [...] Read more.
The rigid-backbone bidentate ligands Indoline-2-carboxylic acid (IndoliH) and Indole-2-carboxylic acid (IndolH) were evaluated for rhodium(I). IndoliH formed [Rh(Indoli)(CO)(PPh3)] (A2), while IndolH yielded the novel dinuclear [Rh1(Indol’)(CO)(PPh3)Rh2(CO)(PPh3)2] (B2) complex (Indol’ = Indol2−), which were characterized by SCXRD. In B2, the Rh1(I) fragment [Rh1(Indol’)(CO)(PPh3)] (bidentate N,O-Indol) exhibits a square-planar geometry, while Rh2(I) shows a ‘Vaska’-type trans-[O-Rh2(PPh3)2(CO)] configuration (bridging the carboxylate ‘oxo’ O atom of Indol2−). The oxidative addition of MeI to A2 and B2 via time-resolved FT-IR, NMR, and UV/Vis analyses indicated only Rh(III)-alkyl species (A3/B3) as products (no migratory insertion). Variable temperature kinetics confirmed an associative mechanism for A2 via an equilibrium-based pathway (ΔH≠ = (21 ± 1) kJ mol−1; ΔS≠ = (−209 ± 4) J K−1mol−1), with a smaller contribution from a reverse reductive elimination/solvent pathway. The dinuclear complex B2 showed the oxidative addition of MeI only at Rh1(I), which formed a Rh(III)-alkyl, but cleaved the bridged Rh2(I) site, yielding trans-[RhI(PPh3)2(I)(CO)] (5B) as a secondary product. A significantly smaller negative activation entropy [ΔH≠ = (73.0 ± 1.2) kJ mol−1; ΔS≠ = (−21 ± 4) J K−1mol−1] via a more complex/potential interchange mechanism (the contribution of ΔS≠ to the Gibbs free energy of activation, ΔG≠, only ±10%) was inferred, contrary to the entropy-driven oxidative addition of MeI to A2 (the contribution of ΔS≠ to ΔG≠ ± 75%). Full article
(This article belongs to the Special Issue Synergy between Main Group and Transition Metal Chemistry)
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9 pages, 3240 KiB  
Article
Mesoporous Silica Nanoparticles for pH-Responsive Delivery of Iridium Metallotherapeutics and Treatment of Glioblastoma Multiforme
by Nikola Ž. Knežević, Nebojša Ilić and Goran N. Kaluđerović
Inorganics 2022, 10(12), 250; https://doi.org/10.3390/inorganics10120250 - 08 Dec 2022
Viewed by 1911
Abstract
Using nanoparticles for controlled drug delivery to cancer, in response to its weakly acidic environment, represents a promising approach toward increasing the effectiveness and reducing the adverse effects of cancer therapy. Hence, the aim of this study is to construct novel mesoporous silica [...] Read more.
Using nanoparticles for controlled drug delivery to cancer, in response to its weakly acidic environment, represents a promising approach toward increasing the effectiveness and reducing the adverse effects of cancer therapy. Hence, the aim of this study is to construct novel mesoporous silica nanoparticle (MSN)-based acidification-responsive drug delivery systems for targeted cancer therapy. Herein, the surface of MSN is covalently functionalized with Ir(III)-based complex through a pH-cleavable hydrazone-based linker and characterized by nitrogen sorption, SEM, FTIR, EDS, TGA, DSC, DLS, and zeta potential measurements. Enhanced release of Ir(III)-complexes is evidenced by UV/VIS spectroscopy at the weakly acidic environments (pH 5 and pH 6) in comparison to the release at physiological conditions. The in vitro toxicity of the prepared materials is tested on healthy MRC-5 cells while their potential for the efficient treatment of glioblastoma multiforme is demonstrated on the U251 cell line. Full article
(This article belongs to the Special Issue Inorganic Nanoparticles in Cancer Therapy II)
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12 pages, 7680 KiB  
Article
Synthesis and Structure of ZnO-Decorated Graphitic Carbon Nitride (g-C3N4) with Improved Photocatalytic Activity under Visible Light
by Maria I. Chebanenko, Sofia M. Tikhanova, Vladimir N. Nevedomskiy and Vadim I. Popkov
Inorganics 2022, 10(12), 249; https://doi.org/10.3390/inorganics10120249 - 08 Dec 2022
Cited by 5 | Viewed by 1889
Abstract
The volume of dye production in the chemical industry is growing rapidly every year. Given the global importance of clean water resources, new wastewater treatment solutions are required. Utilizing photocatalysis by harvesting solar energy represents a facile and promising solution for removing dangerous [...] Read more.
The volume of dye production in the chemical industry is growing rapidly every year. Given the global importance of clean water resources, new wastewater treatment solutions are required. Utilizing photocatalysis by harvesting solar energy represents a facile and promising solution for removing dangerous pollutants. This study reports the possibility of increasing the photocatalytic activity of g-C3N4 by creating nanocomposites with ZnO. Exfoliated g-C3N4/ZnO nanocomposites were synthesized by heat treatment of urea and subsequent ultrasonic exfoliation of the colloidal solution by introducing zinc acetate. The uniformity of the distribution of ZnO nanoparticles is confirmed by the method of elemental mapping. The obtained X-ray diffractograms of the obtained nanocomposites show typical X-ray reflections for g-C3N4 and ZnO. It was found that the introduction of oxide into g-C3N4 leads to an increase in the specific surface area values due to the developed ZnO surface. The maximum value of the specific surface area was obtained for a sample containing 7.5% ZnO and was 75.2 m2/g. The g-C3N4/7.5% ZnO sample also demonstrated increased photocatalytic activity during the decomposition of methylene blue under the influence of visible light, which led to a twofold increase in the reaction rate compared to initial g-C3N4. Full article
(This article belongs to the Special Issue New Advances into Nanostructured Oxides)
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12 pages, 10310 KiB  
Article
Experience of Using DLS to Study the Particle Sizes of Active Component in the Catalysts Based on the Oxide and Non-Oxide Supports
by Yurii V. Larichev
Inorganics 2022, 10(12), 248; https://doi.org/10.3390/inorganics10120248 - 08 Dec 2022
Cited by 1 | Viewed by 2113
Abstract
The present study reports the use of the dynamic light scattering (DLS) method to analyze metal nanoparticle sizes in supported catalysts (as a model system for different metal-oxide nanocomposites, ceramics, etc.). The selective dissolution of matrices has been used to transform solids to [...] Read more.
The present study reports the use of the dynamic light scattering (DLS) method to analyze metal nanoparticle sizes in supported catalysts (as a model system for different metal-oxide nanocomposites, ceramics, etc.). The selective dissolution of matrices has been used to transform solids to sols for DLS analysis. DLS/STS (from solid to sol) technique was tested on a wide number of different sets of supported metal catalysts (Pt, Pd, Ru metals and Al2O3, SiO2, TiO2, C3N4, carbon and polymers as supports). The transmission electron microscopy and X-ray diffraction (TEM/XRD) results for the initial supported catalysts and the DLS results for the sols prepared from them showed good agreement with each other. Moreover, it has been shown that this approach can identify the minor contamination of catalysts by large particles or aggregates which are difficult to detect by TEM/XRD. Full article
(This article belongs to the Special Issue Oxide Optical Ceramics and Precursor Powders Preparation for Luminescence and Laser Applications)
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10 pages, 1017 KiB  
Article
Palladium(II) and Platinum(II) Deprotonated Diaminocarbene Complexes Based on N-(2-Pyridyl)ureas with Oxadiazole Periphery
by Kirill K. Geyl, Svetlana O. Baykova, Pavel A. Andoskin, Vladimir V. Sharoyko, Anastasiya A. Eliseeva, Sergey V. Baykov, Konstantin N. Semenov and Vadim P. Boyarskiy
Inorganics 2022, 10(12), 247; https://doi.org/10.3390/inorganics10120247 - 07 Dec 2022
Cited by 6 | Viewed by 1297
Abstract
Metal mediated coupling of isocyanides with substituted N-(pyridine-2-yl) ureas was first used to incorporate privileged biological motifs into platinum metal complexes. We synthesized two palladium(II) and two platinum(II) cyclometallated species with oxadiazole cores. The compounds were isolated in good yields (61–73%) and [...] Read more.
Metal mediated coupling of isocyanides with substituted N-(pyridine-2-yl) ureas was first used to incorporate privileged biological motifs into platinum metal complexes. We synthesized two palladium(II) and two platinum(II) cyclometallated species with oxadiazole cores. The compounds were isolated in good yields (61–73%) and characterized by high-resolution mass spectrometry and 1H, 13C, and 195Pt NMR spectroscopies. The structures of three complexes were additionally elucidated by X-ray diffraction analysis. These complexes indeed showed cytotoxic activity. The species bearing the 1,3,4-oxadiazole moiety exhibit more potency than the ones with the 1,2,4-oxadiazole ring. Particularly, the cytotoxic effect of both 1,3,4-oxadiazole-based complexes towards T98G cells significantly exceeds the common antitumor metal-drug cisplatin. Full article
(This article belongs to the Special Issue Platinum Group Metals and Their Complexes: Synthesis, Characteristics and Potential Medical Applications)
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14 pages, 1915 KiB  
Article
Organoselenocyanates Tethered Methyl Anthranilate Hybrids with Promising Anticancer, Antimicrobial, and Antioxidant Activities
by Batool Al-Abdallah, Yasair S. Al-Faiyz and Saad Shaaban
Inorganics 2022, 10(12), 246; https://doi.org/10.3390/inorganics10120246 - 07 Dec 2022
Cited by 3 | Viewed by 1377
Abstract
Novel methyl anthranilate-based organoselenocyanate hybrids were developed, and their structures were confirmed by the state-of-the-art spectroscopic techniques. Their antimicrobial potency was estimated against various microbial strains (e.g., Candida albicans, Escherichia coli, and Staphylococcus aureus). The S. aureus and C. albicans strains [...] Read more.
Novel methyl anthranilate-based organoselenocyanate hybrids were developed, and their structures were confirmed by the state-of-the-art spectroscopic techniques. Their antimicrobial potency was estimated against various microbial strains (e.g., Candida albicans, Escherichia coli, and Staphylococcus aureus). The S. aureus and C. albicans strains were more sensitive than E. coli toward the organoselenocyanates. Interestingly, the azoic derivatives 4 and 9, methyl ester 6, and phenoxy acetamide 15 showed promising antimicrobial activity. Moreover, the antitumor potential was estimated against liver and breast carcinomas, as well as primary fibroblasts. Interestingly, the anticancer properties were more pronounced in the HepG2 cells. The organoselenocyanates 4, 6, 9, 10, and 15 showed interesting anti-HepG2 cytotoxic patterns. Additionally, organoselenocyanates 3, 4, and 10 exhibited promising antioxidant activities in the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid and 2,2-diphenyl-1-picrylhydrazyl in vitro assays compared to ascorbic acid. These data point to promising antimicrobial, anticancer, and antioxidant activities of organoselenocyanates 6, 9, and 15 warrant further studies. Full article
(This article belongs to the Special Issue Advances in the Domain of Organometallic Antioxidant and Anticancer Agents)
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12 pages, 4959 KiB  
Article
Manganese(II) Bromide Compound with Diprotonated 1-Hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole: Dual Emission and the Effect of Proton Transfers
by Alexey S. Berezin, Boris Selivanov, Andrey Danilenko, Aleksandr Sukhikh and Andrey Komarovskikh
Inorganics 2022, 10(12), 245; https://doi.org/10.3390/inorganics10120245 - 06 Dec 2022
Cited by 7 | Viewed by 1482
Abstract
An organic–inorganic cation–anion manganese(II) tetrabromide compound with diprotonated 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole, [H3L][MnBr4][H2O], has been synthesized and investigated. The compound has a few possible pathways for proton transfers, which play an important role in the observed luminescence, optical, and magnetic [...] Read more.
An organic–inorganic cation–anion manganese(II) tetrabromide compound with diprotonated 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole, [H3L][MnBr4][H2O], has been synthesized and investigated. The compound has a few possible pathways for proton transfers, which play an important role in the observed luminescence, optical, and magnetic properties. The proton transfers result in the appearance of two-band luminescence. One band is caused by the Mn(II) d-d transitions. The other band is caused by the transition from the triplet state of organic cation and the d-d transition of manganese(II) coupled through {[H3L]}-{[MnBr4]}-{[H2O]} vibrations. The optical absorption spectra of [H3L][MnBr4][H2O] indicate the presence of two direct and one indirect band transitions. The reason for the two-band luminescence and complex optical absorption in [H3L][MnBr4][H2O] were additionally considered using the DFT calculations. Full article
(This article belongs to the Special Issue Recent Advances in the Synthesis and Luminescence Properties of Metal Complexes)
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20 pages, 1810 KiB  
Review
Therapeutic Properties of Vanadium Complexes
by Abeer A. Sharfalddin, Inas M. Al-Younis, Hamdoon A. Mohammed, Manel Dhahri, Fouzi Mouffouk, Hijazi Abu Ali, Md. Jamir Anwar, Kamal A. Qureshi, Mostafa A. Hussien, Mawadda Alghrably, Mariusz Jaremko, Noura Alasmael, Joanna Izabela Lachowicz and Abdul-Hamid Emwas
Inorganics 2022, 10(12), 244; https://doi.org/10.3390/inorganics10120244 - 06 Dec 2022
Cited by 20 | Viewed by 3432
Abstract
Vanadium is a hard, silver-grey transition metal found in at least 60 minerals and fossil fuel deposits. Its oxide and other vanadium salts are toxic to humans, but the toxic effects depend on the vanadium form, dose, exposure duration, and route of intoxication. [...] Read more.
Vanadium is a hard, silver-grey transition metal found in at least 60 minerals and fossil fuel deposits. Its oxide and other vanadium salts are toxic to humans, but the toxic effects depend on the vanadium form, dose, exposure duration, and route of intoxication. Vanadium is used by some life forms as an active center in enzymes, such as the vanadium bromoperoxidase of ocean algae and nitrogenases of bacteria. The structure and biochemistry of vanadate resemble those of phosphate, hence vanadate can be regarded as a phosphate competitor in a variety of biochemical enzymes such as kinases and phosphatases. In this review, we describe the biochemical pathways regulated by vanadium compounds and their potential therapeutic benefits for a range of disorders including type 2 diabetes, cancer, cardiovascular disease, and microbial pathology. Full article
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12 pages, 2818 KiB  
Article
The Electrophoretic Deposition of Nanopowders Based on Yttrium Oxide for Bulk Ceramics Fabrication
by Elena Kalinina and Maxim Ivanov
Inorganics 2022, 10(12), 243; https://doi.org/10.3390/inorganics10120243 - 06 Dec 2022
Cited by 2 | Viewed by 1195
Abstract
In the present work, a study was carried out to investigate the key factors that determine the uniformity, mass, thickness, and density of compacts obtained from nanopowders of solid solutions of yttrium and lanthanum oxides ((LaxY1−x)2O3 [...] Read more.
In the present work, a study was carried out to investigate the key factors that determine the uniformity, mass, thickness, and density of compacts obtained from nanopowders of solid solutions of yttrium and lanthanum oxides ((LaxY1−x)2O3) with the help of the electrophoretic deposition (EPD). Nanopowders were obtained by laser ablation of a mixture of powders of yttrium oxide and lanthanum oxide in air. The implemented mechanisms of the EPD and factors of stability of alcohol suspensions are analyzed. It has been shown that acetylacetone with a concentration of 1 mg/m2 can be used as a dispersant for stabilization of isopropanol suspensions of the nanoparticles during the EPD. It was shown that the maximum density of dry compacts with a thickness of 2.4 mm reaches 37% of theoretical when EPD is performed in vertical direction from a suspension of nanopowders with addition of acetylacetone. Full article
(This article belongs to the Special Issue Oxide Optical Ceramics and Precursor Powders Preparation for Luminescence and Laser Applications)
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13 pages, 2906 KiB  
Article
Dissolution Performance of Carbon/Hydroxyapatite Nanocomposite Prepared from Fish Scales
by Umaporn Sittitut, Junya Jettanasen, Sitthisuntorn Supothina and Ramida Rattanakam
Inorganics 2022, 10(12), 242; https://doi.org/10.3390/inorganics10120242 - 05 Dec 2022
Cited by 3 | Viewed by 1566
Abstract
The utilization of waste as raw materials in the production of functional materials is a growing area of interest to promote global sustainable growth. This work studied the microstructure, chemical properties, and phosphorus (P) dissolution efficiency of carbon/hydroxyapatite (HAP) nanocomposites derived from fish [...] Read more.
The utilization of waste as raw materials in the production of functional materials is a growing area of interest to promote global sustainable growth. This work studied the microstructure, chemical properties, and phosphorus (P) dissolution efficiency of carbon/hydroxyapatite (HAP) nanocomposites derived from fish scale wastes, namely FSBCs. Tilapia scales were pyrolyzed at different temperatures (450–600 °C) and the dissolution performance of the biochars in acidic media was evaluated. The pyrolysis of fish scales yielded biochars which are carbon/HAP nanocomposites of which the characteristics, including the specific surface area, carbon content, degree of crystallinity of HAP, and the degree of CO32− substitution in HAP crystals, were dependent on the pyrolysis temperature and had an influence on the dissolution efficiency. P dissolution experiments suggested that the specific surface area and the presence of carbon in the composite played an important role during the dissolution process. The presence of the organic residues on the carbon could potentially block the calcium sites on HAP from citric acid and lower the dissolution efficiency. The ratio of CO32−/PO43− substitution in HAP also affected the dissolubility of FSBCs. The manipulation of their surface area and the CO32−/PO43− ratio of these materials would allow us to increase its solubility, which could benefit a prospective application such as P fertilizer production. Full article
(This article belongs to the Section Inorganic Materials)
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10 pages, 5481 KiB  
Article
Self-Cleaning and Antibacterial Properties of the Cement Mortar with ZnO/Hydroxyapatite Powders
by Ana-Maria Mocioiu, Ileana Mohanu, Roxana Mioara Piticescu, Ioan Albert Tudor, Ionela Petre, Mihai Ghiță, Andreea Nicoleta Ghiță, Miruna Adriana Ioța, Nicoleta Vitan, Mădălin Enache and Simona Neagu
Inorganics 2022, 10(12), 241; https://doi.org/10.3390/inorganics10120241 - 05 Dec 2022
Cited by 2 | Viewed by 1390
Abstract
According to literature data, different micro- and nanopowders have been used as a partial substitute for cement mortar due to their small size and large specific surface area. The aim of the work is to develop innovative materials based on cement mortar with [...] Read more.
According to literature data, different micro- and nanopowders have been used as a partial substitute for cement mortar due to their small size and large specific surface area. The aim of the work is to develop innovative materials based on cement mortar with antibacterial and self-cleaning properties, which can be used in the long-term maintenance of clean spaces. First, zinc oxide/hydroxyapatite (ZnO/Hap) powder denoted as ZH was synthesized by the hydrothermal method; then it was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM)/ energy dispersive spectroscopy (EDS), and adsorption–desorption isotherms. The second step was the cement mortar preparation: one plain, denoted E, and one with ZH powder inside, denoted MZH. Both mortars were subjected to self-cleaning and antibacterial tests. In the self-cleaning tests, two concentrated solutions of rhodamine B and methylene blue were used. MZH showed a better decolorating after 24 h of UV light than plain cement mortar denoted E for both solutions. In order to highlight the antibacterial effect of cement mortars on some strains of Gram-positive and Gram-negative bacteria, the direct contact method was used. The study revealed that, after 24 h of incubation, the planktonic growth of the E. coli strain is significantly inhibited in the presence of the MZH sample, compared to the control strain. MZH cement mortar exhibits a better growth inhibitory property than the plain cement mortar E. Full article
(This article belongs to the Special Issue Novel Functional Ceramics)
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9 pages, 3711 KiB  
Article
Synthesis of Y3Al5O12:Ce Powders for X-ray Luminescent Diamond Composites
by Sergey V. Kuznetsov, Vadim S. Sedov, Artem K. Martyanov, Dmitrii S. Vakalov, Ludmila V. Tarala, Ivan A. Tiazhelov and Kirill N. Boldyrev
Inorganics 2022, 10(12), 240; https://doi.org/10.3390/inorganics10120240 - 05 Dec 2022
Cited by 3 | Viewed by 1079
Abstract
A concentration series of Y3Al5O12:Ce solid solutions were prepared, and the composition demonstrating the highest X-ray luminescence intensity of cerium was identified. Based on the best composition, a series of luminescent diamond–Y3Al5O12 [...] Read more.
A concentration series of Y3Al5O12:Ce solid solutions were prepared, and the composition demonstrating the highest X-ray luminescence intensity of cerium was identified. Based on the best composition, a series of luminescent diamond–Y3Al5O12:Ce composite films were synthesized using microwave plasma-assisted chemical vapor deposition (CVD) in methane–hydrogen gas mixtures. Variations in the amounts of the embedded Y3Al5O12:Ce powders allowed for the fine-tuning of the luminescence intensity of the composite films. Full article
(This article belongs to the Special Issue Oxide Optical Ceramics and Precursor Powders Preparation for Luminescence and Laser Applications)
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13 pages, 2723 KiB  
Article
Regioselective One-Pot Synthesis of Novel Functionalized Organoselenium Compound by Bis-Alkoxyselenenylation of Alkenes with Selenium Dibromide and Alcohols
by Vladimir A. Potapov, Maxim V. Musalov, Alfiya G. Khabibulina, Arkady A. Maylyan, Tatyana N. Borodina, Sergey V. Zinchenko and Svetlana V. Amosova
Inorganics 2022, 10(12), 239; https://doi.org/10.3390/inorganics10120239 - 05 Dec 2022
Cited by 2 | Viewed by 1335
Abstract
The one-pot efficient synthesis of novel functionalized organoselenium compound by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols was developed. The reaction of the selenium dibromide with cyclopentene or cyclohexene in the system alcohol/sodium bicarbonate/methylene chloride at room temperature afforded bis(2-alkoxycycloalkyl) selenides in [...] Read more.
The one-pot efficient synthesis of novel functionalized organoselenium compound by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols was developed. The reaction of the selenium dibromide with cyclopentene or cyclohexene in the system alcohol/sodium bicarbonate/methylene chloride at room temperature afforded bis(2-alkoxycycloalkyl) selenides in 90–99% yields. The regioselective and efficient method for bis-alkoxylation of terminal alkenes was developed based on the addition of selenium dibromide with 1-alkenes in acetonitrile followed by refluxing of addition products in alcohols in the presence of traces of sulfuric acid. This method made it possible to selectively obtain bis(2-alkoxyalkyl) selenides in 94–98% yields. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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36 pages, 10007 KiB  
Review
Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)
by Evgenii Yu. Matveev, Varvara V. Avdeeva, Konstantin Yu. Zhizhin, Elena A. Malinina and Nikolay T. Kuznetsov
Inorganics 2022, 10(12), 238; https://doi.org/10.3390/inorganics10120238 - 02 Dec 2022
Cited by 30 | Viewed by 1928
Abstract
This review systematizes data on the coordination ability of mono- and disubstituted derivatives of boron cluster anions and carboranes in complexation with transition metals. Boron clusters anions [BnHn]2–, monocarborane anions [CBnHn–1]– [...] Read more.
This review systematizes data on the coordination ability of mono- and disubstituted derivatives of boron cluster anions and carboranes in complexation with transition metals. Boron clusters anions [BnHn]2–, monocarborane anions [CBnHn–1]–, and dicarboranes [C2BnHn–2] (with non-functionalized carbon atoms) (n = 10, 12) containing the B–X exo-polyhedral bonds (X = N, O, S, Hal) are discussed. Synthesis and structural features of complexes known to date are described. The effect of complexing metal and substituent attached to the boron cage on the composition and structures of the final complexes is analyzed. It has been established that substituted derivatives of boron cluster anions and carboranes can act as both ligands and counterions. A complexing agent can coordinate substituted derivatives of the boron cluster anions due to three-center two-electron 3c2e MHB bonds, by the substituent functional groups, or a mixed type of coordination can be realized, through the BH groups of the boron cage and the substituent. As for B-substituted carboranes, complexes with coordinated substituents or salts with non-coordinated carborane derivatives have been isolated; compounds with MHB bonding are not characteristic of carboranes. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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16 pages, 3477 KiB  
Article
Spontaneous Release of Metalloradicals and Coordinatively Unsaturated Species in Asymmetric Iridium Dimers to Promote C-N Bond Formation
by Tsun-Ren Chen, Yi-Sheng Chen, Chia-Ying Li, Yen-Hsing Lin and Yu-Tung Chen
Inorganics 2022, 10(12), 237; https://doi.org/10.3390/inorganics10120237 - 02 Dec 2022
Cited by 1 | Viewed by 1130
Abstract
An unusual iridium dimer 1, [(4-cpbo)Ir(μ-Cl)(μ-O)Ir(4-cpbo)] (4-cpbo = 4-chlorophenylbenzoxazolato-N,C2), was obtained by the oxidative addition of oxygen and reductive elimination of chlorine from a precursor [(4-cpbo)2Ir(μ-Cl)]2. This iridium dimer 1 has a metastable structure with an [...] Read more.
An unusual iridium dimer 1, [(4-cpbo)Ir(μ-Cl)(μ-O)Ir(4-cpbo)] (4-cpbo = 4-chlorophenylbenzoxazolato-N,C2), was obtained by the oxidative addition of oxygen and reductive elimination of chlorine from a precursor [(4-cpbo)2Ir(μ-Cl)]2. This iridium dimer 1 has a metastable structure with an asymmetric bridge, can spontaneously release metalloradicals and coordinatively unsaturated species in solution at room temperature, and exhibits high catalytic ability for synthetic applications. Full article
(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)
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11 pages, 2336 KiB  
Article
Rich CuO Nanowires Fabrication via Laser Post-Treatment of Laser-Textured Copper Substrate
by Zhekun Chen, Gongfa Yuan, Rui Zhou, Weipeng Huang and Minghui Hong
Inorganics 2022, 10(12), 236; https://doi.org/10.3390/inorganics10120236 - 02 Dec 2022
Viewed by 1366
Abstract
The superhydrophobic and anti-icing properties of copper-based materials have been widely concerned. Laser texturing followed by thermal oxidation is a method to prepare durable CuO nanowires on Cu substrate. Rich CuO nanowires on micro-structures are required to meet its applications for anti-icing based [...] Read more.
The superhydrophobic and anti-icing properties of copper-based materials have been widely concerned. Laser texturing followed by thermal oxidation is a method to prepare durable CuO nanowires on Cu substrate. Rich CuO nanowires on micro-structures are required to meet its applications for anti-icing based on sustaining better Cassie–Baxter state stability. In this paper, dense CuO nanowires are obtained by additional laser post-treatment between the laser texturing and thermal oxidation. Uniform Cu2O and CuO layers form on the micro-structures by the laser post-treatment, which serves as the precursors for the growth of nanowires. The density of CuO nanowire increases from 44.3% to 61.4%, resulting in excellent superhydrophobicity and anti-icing performance. The delayed freezing time increases from 17 s to 1519 s at the temperature of −10 °C, which is more than 80 times longer compared to pure Cu substrate. The resulting anti-icing property shows durability through icing–melting cycles and taping tests. This feasible method opens new possibilities for enhanced anti-icing property on copper-based equipment used in low-temperature environments. Full article
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