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Inorganics, Volume 12, Issue 6 (June 2024) – 34 articles

Cover Story (view full-size image): A synthetic study was conducted to explore the reactivity towards tetrabutylammonium cyanide of a series of dinuclear bis-cyclopentadienyl carbonyl complexes of iron and ruthenium, containing a varying unsaturated hydrocarbyl ligand, occupying a bridging coordination site. Depending on the distinct cases, cyanide addition occurs at either the metal centers or the hydrocarbyl moiety, and subsequent intramolecular cyanide migration can be thermally induced, directed by the cooperativity of the dimetallic framework. It was revealed that IR and NMR spectroscopy are potent tools to elucidate the outcomes of the reactions, with DFT calculations assisting in understanding the structural and thermodynamic aspects. View this paper
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15 pages, 4407 KiB  
Article
Palladium-Catalyzed Cross-Coupling Reaction via C–H Activation of Furanyl and Thiofuranyl Substrates
by Neslihan Şahin, İsmail Özdemir and David Sémeril
Inorganics 2024, 12(6), 175; https://doi.org/10.3390/inorganics12060175 - 20 Jun 2024
Viewed by 242
Abstract
The present study explores the potential of four NHC-palladium(II) complexes derived from (Z)- or (E)-styryl-N-alkylbenzimidazolium salts, namely trans-dichloro-[(Z)-1-styryl- 3-benzyl-benzimidazol-2-yliden]pyridine palladium(II) (6), trans-dichloro-[(E)-1-styryl-3-benzyl- benzimidazol-2-yliden]pyridine palladium(II) (7), trans-dichloro-[( [...] Read more.
The present study explores the potential of four NHC-palladium(II) complexes derived from (Z)- or (E)-styryl-N-alkylbenzimidazolium salts, namely trans-dichloro-[(Z)-1-styryl- 3-benzyl-benzimidazol-2-yliden]pyridine palladium(II) (6), trans-dichloro-[(E)-1-styryl-3-benzyl- benzimidazol-2-yliden]pyridine palladium(II) (7), trans-dichloro-[(Z)-1-styryl-3-(3-fluorobenzyl)- benzimidazol-2-yliden]pyridine palladium(II) (8) and trans-dichloro-[(E)-1-styryl-3- (3-fluorobenzyl)-benzimidazol-2-yliden]pyridine palladium(II) (9), to be use as pre-catalysts for the cross-coupling reactions between furanyl or thiofuranyl derivatives and arylbromides via the C–H activation of the heterocycles. The structures of the four Pd(II) complexes have been elucidated through the use of multinuclear NMR, FT-IR and mass spectroscopy. Furthermore, the cis or trans conformation of the styryl substituents and the geometry of two different compounds was substantiated by single-crystal X-ray diffraction, which was carried out on organometallic species 6, 8 and 9. After the optimization of catalytic conditions, which was carried out with 1 mol% of pre-catalyst with KOAc as a base in dimethylacetamide at 120 °C for 3 h, complex 6 proved to be the most effective pre-catalyst agent, with full or quasi full conversions being observed in the cross-coupling of 4-bromoacetophenone with 2-butylfuran, 1-(2-furanyl)-ethanone, furfuryl acetate, furfural, 1-(2-thienyl)-ethanone, thenaldehyde and 2-methylthiophene. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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9 pages, 5149 KiB  
Article
Some Aspects of Hot Carrier Photocurrent across GaAs p-n Junction
by Steponas Ašmontas, Oleksandr Masalskyi, Ihor Zharchenko, Algirdas Sužiedėlis and Jonas Gradauskas
Inorganics 2024, 12(6), 174; https://doi.org/10.3390/inorganics12060174 - 20 Jun 2024
Viewed by 210
Abstract
The photocurrent across crystalline GaAs p-n junction induced by Nd:YAG laser radiation was investigated experimentally. It is established that the displacement current is dominant at reverse and low forward bias voltages in the case of pulsed excitation. This indicates that hot carriers do [...] Read more.
The photocurrent across crystalline GaAs p-n junction induced by Nd:YAG laser radiation was investigated experimentally. It is established that the displacement current is dominant at reverse and low forward bias voltages in the case of pulsed excitation. This indicates that hot carriers do not have enough energy to overcome the p-n junction until the forward bias significantly reduces the potential barrier. At a sufficiently high forward bias, the photocurrent is determined by the diffusion of hot carriers across the p-n junction. The current–voltage (I-V) characteristics measured at different crystal lattice temperatures show that the heating of carriers by laser radiation increases with a drop in crystal lattice temperature. This study proposes a novel model for evaluating carrier temperature based on the temperature coefficient of the I-V characteristic. It is demonstrated that the heating of carriers by light diminishes the conversion efficiency of a solar cell, not only through thermalisation but also because of the conflicting interactions between the hot carrier and conventional photocurrents, which exhibit opposite polarities. These findings contribute to an understanding of hot carrier phenomena in photovoltaic devices and may prompt a revision of the intrinsic losses in solar cells. Full article
(This article belongs to the Special Issue Optical and Quantum Electronics: Physics and Materials)
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11 pages, 4354 KiB  
Article
Direct Synthesis of C-Substituted [RC(O)CH2-CB11H11] Carborate Anions
by Vanessa C. Barra, Eduard Bernhardt, Sarah Fellinger, Carsten Jenne and Shiomi S. Langenbach
Inorganics 2024, 12(6), 173; https://doi.org/10.3390/inorganics12060173 - 19 Jun 2024
Viewed by 263
Abstract
A new synthetic method for the synthesis of C-substituted [RC(O)CH2-CB11H11] carborate anions has been developed. The reaction of [closo-B11H11]2− with terminal alkynes in the presence of a copper [...] Read more.
A new synthetic method for the synthesis of C-substituted [RC(O)CH2-CB11H11] carborate anions has been developed. The reaction of [closo-B11H11]2− with terminal alkynes in the presence of a copper catalyst leads to insertion into the boron cluster, and C-substituted [RC(O)CH2-CB11H11] carborate anions are formed. These reactions are strongly dependent on the reaction conditions, the solvents, and the alkynes used. The alkynes HCCCO2Et, HCCCO2Me, and HCCCONH2 lead to the formation of [NH2C(O)CH2-CB11H11] as the final product in aqueous ammonia solution. In contrast, the reaction using the alkyne HCCCOMe yields [MeC(O)CH2-CB11H11]. The products have been fully characterized by multinuclear NMR and IR spectroscopy as well as mass spectrometry. The crystal structures of K[NH2C(O)CH2-CB11H11] and [NEt3CH2Cl][NH2C(O)CH2-CB11H11] have been determined. Full article
(This article belongs to the Special Issue State-of-the-Art Inorganic Chemistry in Germany)
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12 pages, 4063 KiB  
Article
Theoretical Studies on the Insertion Reaction of Polar Olefinic Monomers Mediated by a Scandium Complex
by Xin Wen, Kaipai Ren, Wenzhen Zhang, Guangli Zhou and Yi Luo
Inorganics 2024, 12(6), 172; https://doi.org/10.3390/inorganics12060172 - 19 Jun 2024
Viewed by 196
Abstract
This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory [...] Read more.
This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory (DFT) calculations and multivariate linear regression (MLR) methods. The chain initiation step of the insertion reaction could be described by the poisoning effect and the ease of monomer insertion, which could be represented via the DFT-calculated energy difference between σ- and π-coordination complexes (ΔΔE) and insertion energy barrier (ΔG), respectively. The results indicate that ΔΔE and ΔG can be predicted by only several descriptors using multiple linear regression methods, with a root mean squared error (RMSE) of less than 2.5 kcal/mol. Furthermore, the qualitative analysis of the MLR models provided effective information on the key factors governing the insertion reaction chain initiation. Full article
(This article belongs to the Special Issue Feature Papers in Organometallic Chemistry 2024)
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23 pages, 6782 KiB  
Article
Synthesis of Cobalt(III) Complexes Derived from Pyridoxal: Structural Cleavage Evaluations and In Silico Calculations for Biological Targets
by Liniquer André Fontana, Francisco Mainardi Martins, Josiéli Demetrio Siqueira, Carlos Serpa, Otávio Augusto Chaves and Davi Fernando Back
Inorganics 2024, 12(6), 171; https://doi.org/10.3390/inorganics12060171 - 18 Jun 2024
Viewed by 345
Abstract
This study sought to investigate the synthesis of eight complexes constituted by a cobalt(III) (CoIII) metallic center coordinated to two units of iminic ligands LnC (n = 1–4, L1CL4C), which are derivatives of pyridoxal hydrochloride and anilines with [...] Read more.
This study sought to investigate the synthesis of eight complexes constituted by a cobalt(III) (CoIII) metallic center coordinated to two units of iminic ligands LnC (n = 1–4, L1CL4C), which are derivatives of pyridoxal hydrochloride and anilines with thioether function containing one to four carbons. Depending on the source of the cobalt ion and the addition (or not) of a non-coordinating counterion, complexes with distinct structures may form, being categorized into two series: [CoIII(LnC)(L0C)] (n = 1–4, C1’C4’) with a LnC ligand and a ligand that has a thiolate function which cleaves the C-S(thioether) bond (L0C) and [CoIII(LnC)2]PF6 (n = 1–4, C1C4) with two similar units of the same LnC ligand. The occurrence (or not) of cleavage in the eight complexes was observed by elucidating the solid-state structures by single crystal X-ray diffraction. This exciting method allows the synthesis of CoIII complexes without cleaving the C-S bonds from the ligands, thereby not requiring an inert atmosphere in the reaction systems. The synthesized complexes were evaluated by in silico calculations on viable biological targets such as deoxyribonucleic acid, superoxide dismutase enzyme, human serum albumin, and the structural spike glycoprotein of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) with the receptor binding domain (RBD) in both up and down conformations without and in complex with the cellular receptor angiotensin-converting enzyme 2 (ACE2). Overall, in silico results suggested that all the inorganic complexes under study are potential anticancer/antiviral agents; however, C4 and C4’ are the best candidates for future in vitro assays. Full article
(This article belongs to the Special Issue Evaluation of the Potential Biological Activity of Metallo-Drugs)
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12 pages, 5060 KiB  
Article
Silver Nanoparticle-Immobilized Cotton Fabric Serves as Flexible Surface-Enhanced Raman Scattering Substrate for Detection of Toxin
by Bharat Baruah and Michael Woods
Inorganics 2024, 12(6), 170; https://doi.org/10.3390/inorganics12060170 - 17 Jun 2024
Viewed by 336
Abstract
We designed composite materials containing silver nanoparticles (AgNPs) and cotton fabric (CF). The cellulose in cotton fabric contains -OH groups. These -OH groups were deprotonated by a pretreatment process, and Ag+ ions were allowed to bind. In the consecutive step, the Ag [...] Read more.
We designed composite materials containing silver nanoparticles (AgNPs) and cotton fabric (CF). The cellulose in cotton fabric contains -OH groups. These -OH groups were deprotonated by a pretreatment process, and Ag+ ions were allowed to bind. In the consecutive step, the Ag+ ions were reduced to fiber-bound AgNPs, generating AgNP@CF. Three different AgNP@CF composites were created, varying the concentration of the precursor AgNO3 solution. The composite materials were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), and FTIR spectroscopy. The AgNP@CF composites were assessed for the detection of toxins using the surface-enhanced Raman scattering (SERS) technique. Full article
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14 pages, 11384 KiB  
Article
Low-Temperature Fast Firing Preparation of Zn2TiO4 Crystalline Photovoltaic Glass Ink and Its Properties
by Yongjian Chen, Weixia Dong, Qifu Bao, Tiangui Zhao, Zhipeng Cheng and Yan Xu
Inorganics 2024, 12(6), 169; https://doi.org/10.3390/inorganics12060169 - 17 Jun 2024
Viewed by 479
Abstract
A Zn2TiO4 crystalline photovoltaic glass ink was prepared by fast firing at 700 °C for 5 min by the glass crystallisation method, which effectively improved the reflectivity and acid resistance of the photovoltaic glass ink coating. The phase, morphology and [...] Read more.
A Zn2TiO4 crystalline photovoltaic glass ink was prepared by fast firing at 700 °C for 5 min by the glass crystallisation method, which effectively improved the reflectivity and acid resistance of the photovoltaic glass ink coating. The phase, morphology and properties of the samples were tested by XRD, SEM and UV-vis diffuse reflection, etc. The enhanced reflectivity mechanism was proposed. The results showed that the increase in ZnO/SiO2 ratio reduced the transition temperature (Tg) and crystallisation temperature (Tp) of the glass melt, which could promote the crystallinity of Zn2TiO4 in photovoltaic glass ink coatings and thus improve the acid resistance of photovoltaic glass inks. Significant improvement in reflectance and whiteness is due to the Zn2TiO4 crystallinity growth, which fills in the pores of the ink surface, and TiO2 fillers keep almost the same surface roughness (0.2 µm) and wetting angle (5.2°). Typical samples achieved 89.2% of the whiteness and 88.0% of the reflectance, and the weight loss in acid was 3.9 mg/cm2, which could improve the efficiency of solar power generation. Full article
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15 pages, 12806 KiB  
Review
Cell Metabolomics to Guide the Design of Metal-Based Compounds
by Veronica Ghini
Inorganics 2024, 12(6), 168; https://doi.org/10.3390/inorganics12060168 - 15 Jun 2024
Viewed by 297
Abstract
Despite the increasing interest in the development of novel metal-based compounds for cancer treatment, these molecules are currently poorly characterized in mechanistic terms, due to their multiple macromolecular targets inside the cells. In this review, we show how 1H NMR metabolomics provides [...] Read more.
Despite the increasing interest in the development of novel metal-based compounds for cancer treatment, these molecules are currently poorly characterized in mechanistic terms, due to their multiple macromolecular targets inside the cells. In this review, we show how 1H NMR metabolomics provides a powerful tool to investigate the metabolic perturbations induced by metal-compounds in cells. The chemical identity and concentration of metabolites detected in cell lysates and their respective growth media by NMR can be viewed as a global fingerprint that describes the response to drug treatment. In this framework, the applications of NMR-based metabolomics to study cellular effects induced by the treatment of cells with anticancer metal-based compounds are comprehensively reviewed. Full article
(This article belongs to the Special Issue Rational Design of Pharmacologically Active Metal-Based Compounds)
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12 pages, 2507 KiB  
Article
Investigating the Anticancer Properties of Novel Functionalized Platinum(II)–Terpyridine Complexes
by Roberta Panebianco, Maurizio Viale, Valentina Giglio and Graziella Vecchio
Inorganics 2024, 12(6), 167; https://doi.org/10.3390/inorganics12060167 - 15 Jun 2024
Viewed by 302
Abstract
Novel platinum(II) complexes of 4′-substituted terpyridine ligands were synthesized and characterized. Each complex had a different biomolecule (amine, glucose, biotin and hyaluronic acid) as a targeting motif, potentially improving therapeutic outcomes. We demonstrated that complexes can self-assemble in water into about 150 nm [...] Read more.
Novel platinum(II) complexes of 4′-substituted terpyridine ligands were synthesized and characterized. Each complex had a different biomolecule (amine, glucose, biotin and hyaluronic acid) as a targeting motif, potentially improving therapeutic outcomes. We demonstrated that complexes can self-assemble in water into about 150 nm nanoparticles. Moreover, the complexes were assayed in vitro toward a panel of human cancer cell lines (ovarian adenocarcinoma A2780, lung cancer A549, breast adenocarcinoma MDA-MB-231, neuroblastoma SHSY5Y) to explore the impact of the pendant moiety on the terpyridine toxicity. The platinum complex of terpyridine amine derivative, [Pt(TpyNH2)Cl]Cl, showed the best antiproliferative effect, which was higher than cisplatin and [Pt(Tpy)Cl]Cl. Selective in vitro antiproliferative activity was achieved in A549 cancer cells with the Pt–HAtpy complex. These findings underline the potential of these novel platinum(II) complexes in cancer therapy and highlight the importance of tailored molecular design for achieving enhanced therapeutic effects. Full article
(This article belongs to the Special Issue Evaluation of the Potential Biological Activity of Metallo-Drugs)
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12 pages, 4198 KiB  
Article
Sodium Filling in Superadamantoide Na1.36(Si0.86Ga0.14)2As2.98 and the Mixed Valent Arsenidosilicate-Silicide Li1.5Ga0.9Si3.1As4
by Marlo Schöneich, Lucas G. Balzat, Bettina V. Lotsch and Dirk Johrendt
Inorganics 2024, 12(6), 166; https://doi.org/10.3390/inorganics12060166 - 14 Jun 2024
Viewed by 277
Abstract
Na1.36(Si0.86Ga0.14)2As2.98 and Li1.5Ga0.9Si3.1As4 were synthesized by heating mixtures of the elements at 950 °C. The crystal structures were determined by single crystal X-ray diffraction (Na1.36(Si [...] Read more.
Na1.36(Si0.86Ga0.14)2As2.98 and Li1.5Ga0.9Si3.1As4 were synthesized by heating mixtures of the elements at 950 °C. The crystal structures were determined by single crystal X-ray diffraction (Na1.36(Si0.86Ga0.14)2As2.98: I41/a, Z = 100, a = 19.8772(4) Å, c = 37.652(1) Å; Li1.5Ga0.9Si3.1As4: C2/c, Z = 8, a = 10.8838(6) Å, b = 10.8821(6) Å, c = 13.1591(7) Å). Na1.36(Si0.86Ga0.14)2As2.98 crystallizes similar to NaSi2P3 with interpenetrating networks of vertex-sharing T4 and T5 supertetrahedra. Gallium substitution at the silicon sites increases the charge of the cluster network, which is compensated for by a 36% higher sodium content. Since in contrast to NaSi2P3, all sodium sites are now fully occupied, there is no significant ion mobility, as indicated by 23Na-NMR. Consequently, the total sodium-ion conductivity of Na1.36(Si0.86Ga0.14)2As2.98 amounts to only 1.6(1) × 10−7 S cm−1 and is therefore three orders of magnitude lower than in NaSi2P3. Li1.5Ga0.9Si3.1As4 crystallizes in a new structure type with layers of edge-sharing (Si1−xGax)As4 tetrahedra alternating with layers that contain infinite Sin zigzag chains. Lithium ions reside in channels between the chains, and thus, the structure does not provide three dimensional pathways for ion conduction and the measured total Li-ion conductivity amounts to only 1.3(1) × 10−7 S cm−1. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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13 pages, 3058 KiB  
Article
MOF-Derived Fe2CoSe4@NC and Fe2NiSe4@NC Composite Anode Materials towards High-Performance Na-Ion Storage
by Hangxuan Xie, Wei Zhang, Chao Wang, Shangcheng Zhao, Zhentao Hao, Xiaolian Huang, Kanghua Miao and Xiongwu Kang
Inorganics 2024, 12(6), 165; https://doi.org/10.3390/inorganics12060165 - 12 Jun 2024
Viewed by 472
Abstract
Binary transition metal selenides (BTMSs) are more promising than single transition metal selenides (TMS) as anode materials of sodium-ion batteries (SIBs). However, it is still very challenging to prepare high-performance BTMSs in the pure phase, instead of a mixture of two TMSs. In [...] Read more.
Binary transition metal selenides (BTMSs) are more promising than single transition metal selenides (TMS) as anode materials of sodium-ion batteries (SIBs). However, it is still very challenging to prepare high-performance BTMSs in the pure phase, instead of a mixture of two TMSs. In this study, a binary metal center-based MOF derived selenization strategy was developed to prepare iron–cobalt selenide (Fe2CoSe4@NC) and iron–nickel selenide (Fe2NiSe4@NC) nanocomposites in the single phase and when wrapped with carbon layers. As the anode material of SIBs, Fe2CoSe4@NC exhibits higher long-term cycling performance than Fe2NiSe4@NC, maintaining a capacity of 352 mAh g−1 after 2100 cycles at 1.0 A g−1, which is ascribed to the higher percentage of the nanopores, larger lattice spacing, and faster Na+ diffusion rate in the electrode materials of the former rather than the latter. Full article
(This article belongs to the Special Issue Advanced Electrode Materials for Energy Storage Devices)
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24 pages, 7873 KiB  
Article
CuFe2O4 Nanofiber Incorporated with a Three-Dimensional Graphene Sheet Composite Electrode for Supercapacitor and Electrochemical Sensor Application
by Sivaramakrishnan Vinothini, Arjunan Karthi Keyan, Subramanian Sakthinathan, Te-Wei Chiu and Naratip Vittayakorn
Inorganics 2024, 12(6), 164; https://doi.org/10.3390/inorganics12060164 - 12 Jun 2024
Viewed by 390
Abstract
The demand for regenerative energy and electric automotive applications has grown in recent decades. Supercapacitors have multiple applications in consumer alternative electronic products due to their excellent energy density, rapid charge/discharge time, and safety. CuFe2O4-incorporated three-dimensional graphene sheet (3DGS) [...] Read more.
The demand for regenerative energy and electric automotive applications has grown in recent decades. Supercapacitors have multiple applications in consumer alternative electronic products due to their excellent energy density, rapid charge/discharge time, and safety. CuFe2O4-incorporated three-dimensional graphene sheet (3DGS) nanocomposites were studied by different characterization studies such as X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. The electrochemical studies were based on cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) measurements. As prepared, 3DGS/CuFe2O4 nanocomposites exhibited an excellent surface area, high energy storage with appreciable durability, and excellent electrocatalysis properties. A supercapacitor with 3DGS/CuFe2O4-coated nickel foam (NF) electrodes exhibited an excellent specific capacitance of 488.98 Fg−1, a higher current density, as well as a higher power density. After charge–discharge cycles in a 2.0 M KOH aqueous electrolyte solution, the 3DGS/CuFe2O4/NF electrodes exhibited an outstanding cyclic stability of roughly 95% at 10 Ag−1, indicating that the prepared nanocomposites could have the potential for energy storage applications. Moreover, the 3DGS/CuFe2O4 electrode exhibited an excellent electrochemical detection of chloramphenicol with a detection limit of 0.5 µM, linear range of 5–400 µM, and electrode sensitivity of 3.7478 µA µM−1 cm−2. Full article
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12 pages, 4896 KiB  
Article
Electronic and Steric Effects on Oxygen Reactivities of NiFeSe Complexes Related to O2-Damaged [NiFeSe]-Hydrogenases’ Active Site
by Yuchen Qiao, Enting Xu, Yameng Hao, Xuemei Yang and Ming Ni
Inorganics 2024, 12(6), 163; https://doi.org/10.3390/inorganics12060163 - 10 Jun 2024
Viewed by 346
Abstract
Hydrogen has the potential to serve as a new energy resource, reducing greenhouse gas emissions that contribute to climate change. Natural hydrogenases exhibit impressive catalytic abilities for hydrogen production, but they often lack oxygen tolerance. Oxygen-tolerant hydrogenases can work under oxygen by reacting [...] Read more.
Hydrogen has the potential to serve as a new energy resource, reducing greenhouse gas emissions that contribute to climate change. Natural hydrogenases exhibit impressive catalytic abilities for hydrogen production, but they often lack oxygen tolerance. Oxygen-tolerant hydrogenases can work under oxygen by reacting with oxygen to form inactive states, which can be reactivated to catalytic states by oxygen atom removal. Herein, we synthesized three NiFeSe complexes: (NiSe(CH3)FeCp, NiSe(CH3)FeCp* and NiSe(PhNMe2)FeCp) with features of active sites of [NiFeSe]-H2ases, which are the oxygen-tolerant hydrogenases, and we investigated the influence of electronic and steric factors on the oxygen reaction of these “biomimetic” complexes. In our research, we found that they react with oxygen, forming 1-oxygen species, which is related to the O2-damaged [NiFeSe] active site. Through a comparative analysis of oxygen reactions, we have discovered that electronic factors and steric hindrance on Se play a significant role in determining the oxygen reactivity of NiFe complexes related to hydrogenases’ active sites. Full article
(This article belongs to the Special Issue Metal Complexes Diversity: Synthesis, Conformations, and Bioactivity)
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13 pages, 1157 KiB  
Article
Limited Domain SnSb@N-PC Composite Material as a High-Performance Anode for Sodium Ion Batteries
by Zhaomeng Liu, Hailong Ren, Shizheng Fu, Wentao Yang, Yihua Li, Yang Jiao and Botao Zhang
Inorganics 2024, 12(6), 162; https://doi.org/10.3390/inorganics12060162 - 7 Jun 2024
Viewed by 247
Abstract
Anode materials have a vital influence on the performance of sodium ion batteries. In this paper, SnSb nanoparticles were distributed uniformly in N-doped three-dimensional porous carbon (SnSb@N-PC), which effectively avoided the agglomeration of alloy nanoparticles and greatly improved the capacity retention rate of [...] Read more.
Anode materials have a vital influence on the performance of sodium ion batteries. In this paper, SnSb nanoparticles were distributed uniformly in N-doped three-dimensional porous carbon (SnSb@N-PC), which effectively avoided the agglomeration of alloy nanoparticles and greatly improved the capacity retention rate of SnSb@N-PC. At the same time, the porous carbon substrate brings higher conductivity, larger specific surface area, and more sodium storage sites, which makes the material obtain excellent sodium storage properties. The first discharge-specific capacity of SnSb@N-PC was 846.3 mAh g−1 at the current density of 0.1 A g−1, and the specific capacity remained at 483 mAh g−1 after 100 cycles. Meanwhile, the specific capacity of SnSb@N-PC was kept at 323 mAh g−1 after 400 cycles at a high current density of 1.5 A g−1, which indicated that the recombination of SnSb with porous carbon played a key role in the electrochemical performance of SnSb. The contribution of capacitance contrast capacity was able to reach more than 90% by the cyclic voltammetry (CV) test at high sweep speed, and larger Na+ diffusivity was obtained by the constant current intermittent titration technique (GITT) test, which explains the good rate performance of SnSb@N-PC. Full article
(This article belongs to the Special Issue New Insights in Potassium Ion Batteries: Materials and Properties)
19 pages, 3073 KiB  
Article
Alkali Metal-Ion Binding by a Model Macrocycle Containing a C-I···N Halogen Bonded Network: A DFT Study of C-I···M+ and N···M+ Binding Interactions, M+ = Li+, Na+, K+, and Rb+
by Rubén D. Parra
Inorganics 2024, 12(6), 161; https://doi.org/10.3390/inorganics12060161 - 6 Jun 2024
Viewed by 888
Abstract
The complexation of an alkali metal ion by a model macrocycle is examined using the M05-2X/DGDZVP DFT method. The macrocycle is built by connecting three cyclopenta[b]pyrrole motifs with alternating acetylene and ethylene linkages. Replacing one of the C-H bonds in each motif with [...] Read more.
The complexation of an alkali metal ion by a model macrocycle is examined using the M05-2X/DGDZVP DFT method. The macrocycle is built by connecting three cyclopenta[b]pyrrole motifs with alternating acetylene and ethylene linkages. Replacing one of the C-H bonds in each motif with a C-I bond allows for the formation of three intramolecular C-I···N halogen bonds. Two distinct binding modes were found for the complexation of each metal ion. In one mode, the binding of the ion occurs solely by the iodine atoms, via I···M+ interactions, while maintaining the integrity of the halogen bonds. The complexation energies are in the range −66 to −35 kcal/mol. In the other mode, the binding of the ion includes one nitrogen atom as well, with binding energies in the range of −71 to −38 kcal/mol. In this binding mode, the halogen bond network is weakened. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, the geometries for the transition state structures linking the less stable to the more stable metal ion complexes were obtained, and their calculated Gibbs free energy barriers were found in the range of 1.6 to 1.9 kcal/mol. Full article
(This article belongs to the Special Issue Studies on Metal-Ion Binding by Halogen-Bonded Structures)
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25 pages, 4958 KiB  
Article
Physicochemical and Toxicological Screening of Silver Nanoparticle Biosynthesis from Punica granatum Peel Extract
by Oana Silvana Sarău, Elena-Alina Moacă, Alexandra-Denisa Semenescu, Raluca Dumitru, Alex-Robert Jijie, Marioara Poenaru, Cristina-Adriana Dehelean and Adelina Chevereşan
Inorganics 2024, 12(6), 160; https://doi.org/10.3390/inorganics12060160 - 4 Jun 2024
Viewed by 465
Abstract
Silver nanoparticles (AgNPs) were successfully synthesized via the biological route using a 1 M silver nitrate (AgNO3) aqueous solution and an ethanolic peel extract of Punica granatum (Pg), at 60 °C. The physicochemical analysis revealed the formation of green synthesized Pg-AgNPs [...] Read more.
Silver nanoparticles (AgNPs) were successfully synthesized via the biological route using a 1 M silver nitrate (AgNO3) aqueous solution and an ethanolic peel extract of Punica granatum (Pg), at 60 °C. The physicochemical analysis revealed the formation of green synthesized Pg-AgNPs with a semi-spherical shape, non-uniformly distributed, and a particle size distribution between 5 and 100 nm. As regards the preliminary in vitro toxicological screening, the green synthesized Pg-AgNPs did not significantly affect the neonatal BALB/c epidermal cells’ viability (JB6 Cl 41-5a) at lower concentrations and did not produce visible changes in the morphology of the JB6 Cl 41-5a cells. In contrast, at higher concentrations (>50 μg/mL), the green Pg-AgNPs exhibited an important decrease in cell viability and confluency. In addition, the impact of Pg-AgNPs on cell membrane integrity suggests a potential cytotoxic effect. Contrary to the in vitro assays, after the evaluation of the anti-irritant effect in ovo, the lower concentration of Pg-AgNPs (10 μg/mL) produced hemorrhage and lysis when applied to the chorioallantoic membrane, while at 50 μg/mL, only slight coagulation was observed. Therefore, regarding the in ovo toxicological screening, the higher concentration of the Pg-AgNPs exhibited a better safety profile compared to the lower concentration, as indicated by the irritation score. Full article
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9 pages, 3376 KiB  
Article
Mononuclear Fe(III) Schiff Base Complex with Trans-FeO4N2 Chromophore of o-Aminophenol Origin: Synthesis, Characterisation, Crystal Structure, and Spin State Investigation
by Dawit Tesfaye, Jonas Braun, Mamo Gebrezgiabher, Juraj Kuchár, Juraj Černák, Taju Sani, Abbasher Gismelseed, Tim Hochdörffer, Volker Schünemann, Christopher E. Anson, Annie K. Powell and Madhu Thomas
Inorganics 2024, 12(6), 159; https://doi.org/10.3390/inorganics12060159 - 3 Jun 2024
Viewed by 612
Abstract
A new iron(III) complex (Et3NH)2[Fe(L)2](ClO4)·MeOH (1) where H2L = 2-{(E)-[2-hydroxyphenyl)imino]methyl}phenol has been synthesised and characterised by single crystal XRD, elemental analysis and DC magnetic susceptibility measurements. The dianionic ligands L2− coordinate in [...] Read more.
A new iron(III) complex (Et3NH)2[Fe(L)2](ClO4)·MeOH (1) where H2L = 2-{(E)-[2-hydroxyphenyl)imino]methyl}phenol has been synthesised and characterised by single crystal XRD, elemental analysis and DC magnetic susceptibility measurements. The dianionic ligands L2− coordinate in a tridentate fashion with the Fe(III) through their deprotonated phenolic oxygens and azomethine nitrogen atoms, resulting in a trans-FeO4N2 chromophore. Variable-temperature magnetic measurements were performed between 300 and 5 K under an applied field of 0.1 T and show that 1 is in the high spin state (S = 5/2) over the whole measured temperature range. This is confirmed by Mössbauer spectroscopy at 77 and 300 K. Full article
(This article belongs to the Section Coordination Chemistry)
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25 pages, 5074 KiB  
Article
Evaluation of DNA and BSA-Binding, Nuclease Activity, and Anticancer Properties of New Cu(II) and Ni(II) Complexes with Quinoline-Derived Sulfonamides
by Tamara Liana Topală, Ionel Fizeşan, Andreea-Elena Petru, Alfonso Castiñeiras, Andreea Elena Bodoki, Luminița Simona Oprean, Marcos Escolano and Gloria Alzuet-Piña
Inorganics 2024, 12(6), 158; https://doi.org/10.3390/inorganics12060158 - 1 Jun 2024
Viewed by 232
Abstract
Four complexes of essential metal ions, Cu(II) and Ni(II), with the new sulfonamide ligand N-(pyridin-2-ylmethyl)quinoline-8-sulfonamide (HQSMP) were synthesized and physicochemically and structurally characterized. Complex [Cu(QSMP)Cl]n (2) consists of a polymeric chain formed by distorted square pyramidal units. In 2 [...] Read more.
Four complexes of essential metal ions, Cu(II) and Ni(II), with the new sulfonamide ligand N-(pyridin-2-ylmethyl)quinoline-8-sulfonamide (HQSMP) were synthesized and physicochemically and structurally characterized. Complex [Cu(QSMP)Cl]n (2) consists of a polymeric chain formed by distorted square pyramidal units. In 2, the sulfonamide ligand acts as a bridge coordinating to one Cu(II) through its three N atoms and to another metal ion via one O atom in the sulfonamido group, while the pentacoordinate complex [Cu(QSMP)(C6H5COO)] (3) presents a highly distorted square pyramidal geometry. Complex [Ni(QSMP)(C6H5COO)(CH3OH)][Ni(QSMP)(CH3COO)(CH3OH)] (4) consists of two mononuclear entities containing different anion coligands, either a benzoate or an acetate group. Both units exhibit a distorted octahedral geometry. The interaction of the complexes with CT-DNA was studied by means of UV-Vis and fluorescence spectroscopy, interestingly revealing that the Ni(II) complex presents the highest affinity towards the nucleic acid. Complexes 1 and 2 are able to cleave DNA. Both compounds show promising nuclease activity at relatively low concentrations by mediating the production of a reactive oxygen species (ROS). The interaction of the four complexes with bovine serum albumin (BSA) was also investigated, showing that the compounds can bind to serum proteins. The antitumor potential of complexes 1 and 2 was evaluated against the A549 lung adenocarcinoma cell line, revealing cytotoxic properties that were both dose- and time-dependent. Full article
(This article belongs to the Special Issue Metal-Based Compounds: Relevance for the Biomedical Field)
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14 pages, 2435 KiB  
Article
Hybrid Gold-Based Perovskite Derivatives: Synthesis, Properties, and Prospects in Photovoltaics
by Chang Liu, Xifeng Fu, Zi-Ang Nan, Zilong Zhang, Lingyi Meng and Peng Gao
Inorganics 2024, 12(6), 157; https://doi.org/10.3390/inorganics12060157 - 31 May 2024
Viewed by 279
Abstract
Hybrid gold-based perovskite derivatives typically exhibit low optical bandgaps and high optical absorption coefficients, rendering them promising for photovoltaic applications. In this study, we successfully synthesized six new hybrid gold-based perovskite derivatives, namely [(C6H8N2)(AuI4)(AuI2 [...] Read more.
Hybrid gold-based perovskite derivatives typically exhibit low optical bandgaps and high optical absorption coefficients, rendering them promising for photovoltaic applications. In this study, we successfully synthesized six new hybrid gold-based perovskite derivatives, namely [(C6H8N2)(AuI4)(AuI2)](3AMPY), [(C6H14N2)(AuI4)(AuI2)](3AMP), [(C8H12N)(AuI4)](2PEAI), [(C4H14N2O)(AuI4)2](OBA), [(C6H18N2O2)3(AuI4)4(I3)2](DDA), and [(C10H26N2O3)(AuI4)(I3)](TOTA), through a straightforward and efficient hydrothermal method, achieving millimeter-sized single crystals. The structural analysis of the single crystals revealed variations in crystal structures arising from differences in constituent units and their spatial positioning relationships. First-principles calculations ascertained their high optical absorption coefficients in the visible light spectrum and indirect bandgap properties. Theoretical models indicated that the spectroscopic limited maximum efficiency (SLME) values of 3AMPY, 2PEAI, DDA, and TOTA approached approximately 30% in films of 0.5 μm thickness, signifying their potential candidacy as solar cell absorbers. Full article
(This article belongs to the Special Issue New Semiconductor Materials for Energy Conversion)
14 pages, 8294 KiB  
Article
Orange Peel Biochar–CdS Composites for Photocatalytic Hydrogen Production
by Xiang Li, Yuxin Zang, Jindi Zhang, Lili Zhang, Jing Zhang, Mengyang Huang and Jiaqiang Wang
Inorganics 2024, 12(6), 156; https://doi.org/10.3390/inorganics12060156 - 31 May 2024
Viewed by 242
Abstract
Orange peel biochar (C)-supported cadmium sulfide composites (CdS-C) were prepared by the combination of hydrothermal and calcination methods. The structure and morphology were characterized in detail by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The CdS-C composite with 60% CdS exhibited [...] Read more.
Orange peel biochar (C)-supported cadmium sulfide composites (CdS-C) were prepared by the combination of hydrothermal and calcination methods. The structure and morphology were characterized in detail by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The CdS-C composite with 60% CdS exhibited the highest photocatalytic hydrogen production rate of 7.8 mmol·g−1·h−1, approximately 3.69 times higher than that of synthesized CdS without biochar. These results indicate that biochar derived from orange peel could be a low-cost, renewable, environmentally friendly, and metal-free co-catalyst for CdS, enhancing its photostability. Full article
(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials)
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18 pages, 2935 KiB  
Article
Matrix Effect on Singlet Oxygen Generation Using Methylene Blue as Photosensitizer
by Jianan Xu, Laurent Bonneviot, Yannick Guari, Cyrille Monnereau, Kun Zhang, Albert Poater, Montserrat Rodríguez-Pizarro and Belén Albela
Inorganics 2024, 12(6), 155; https://doi.org/10.3390/inorganics12060155 - 31 May 2024
Viewed by 306
Abstract
Methylene blue (MB) is a well-established and extensively studied photosensitizer for photodynamic therapy (PDT), since it can generate singlet oxygen with a high quantum yield upon irradiation within the phototherapeutic (600–950 nm) window. However, its activity can decrease due to the formation of [...] Read more.
Methylene blue (MB) is a well-established and extensively studied photosensitizer for photodynamic therapy (PDT), since it can generate singlet oxygen with a high quantum yield upon irradiation within the phototherapeutic (600–950 nm) window. However, its activity can decrease due to the formation of dimers or higher aggregates, which can take place in an aqueous solution at relatively high concentrations. The incorporation of this molecule into a matrix can avoid this aggregation and increase its activity relative to PDT. Silica porous nanoparticles are chosen here as a matrix to host MB. The size and pore geometry are tuned in order to decrease MB leaching while maintaining good singlet oxygen generation and colloidal stability for further applications in nanomedicine. In addition, phenyl functions are grafted on the pores of the silica matrix in order to avoid MB aggregation, thereby increasing the activity of the photosensitizer in the singlet oxygen generation. DFT calculations give insight in the structure of the aggregation of the MB units, and the roles of water and organic environments are investigated through time-dependent calculations on UV-vis spectra. Full article
(This article belongs to the Special Issue Women’s Special Issue Series: Inorganics)
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15 pages, 4757 KiB  
Article
N-S-co-Doped Carbon Dot Blue Fluorescence Preparation and Baicalein Detection
by Yujia Cheng, Yan Huang and Guang Yu
Inorganics 2024, 12(6), 154; https://doi.org/10.3390/inorganics12060154 - 31 May 2024
Viewed by 213
Abstract
Carbon dots (CDs) have emerged as significant fluorescent nanomaterials due to their bright, stable fluorescence, good biocompatibility, facile synthesis, etc. They are widely used in various scientific and practical applications, particularly in combination with mesoporous, florescent, or magnetic nanomaterials to enhance their properties. [...] Read more.
Carbon dots (CDs) have emerged as significant fluorescent nanomaterials due to their bright, stable fluorescence, good biocompatibility, facile synthesis, etc. They are widely used in various scientific and practical applications, particularly in combination with mesoporous, florescent, or magnetic nanomaterials to enhance their properties. Recent research has focused on employing CDs and their composites in drug analysis, drug loading, biological imaging, disease diagnosis, and temperature sensing, with a growing interest in their biological and medical applications. In this study, we synthesized blue-fluorescent S, N-co-doped CDs (cys-CDs) using hydrothermal synthesis with L-cysteine and sodium citrate. These resulting cys-CD particles were approximately 3.8 nm in size and exhibited stable fluorescence with a quantum yield of 0.66. By leveraging the fluorescence quenching of the cys-CDs, we developed a rapid and sensitive method for baicalein detection, achieving high sensitivity in the low micromolar range with a detection limit for baicalein of 33 nM. Our investigation revealed that the fluorescence-quenching mechanism involved static quenching and inner-filter effect components. Overall, cys-CDs proved to be effective for accurate quantitative baicalein detection in real-world samples. Full article
(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials)
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13 pages, 4045 KiB  
Article
Ni and Co Catalysts on Interactive Oxide Support for Anion Exchange Membrane Electrolysis Cell (AEMEC)
by Katerina Maksimova-Dimitrova, Borislava Mladenova, Galin Borisov and Evelina Slavcheva
Inorganics 2024, 12(6), 153; https://doi.org/10.3390/inorganics12060153 - 31 May 2024
Viewed by 260
Abstract
The work presents novel composite catalytic materials—Ni and Co deposited on Magneli phase titania—and describes their complex characterization and integration into membrane electrode assemblies to produce hydrogen by electrochemical water splitting in cells with anion exchange membranes (AEMEC). Chemical composition, surface structure, and [...] Read more.
The work presents novel composite catalytic materials—Ni and Co deposited on Magneli phase titania—and describes their complex characterization and integration into membrane electrode assemblies to produce hydrogen by electrochemical water splitting in cells with anion exchange membranes (AEMEC). Chemical composition, surface structure, and morphology were characterized by XRD and SEM analysis. The activity in the evolution of the partial electrode reactions of hydrogen (HER) and oxygen (OER) was assessed in an aqueous alkaline electrolyte (25 wt.% KOH) using linear sweep voltammetry. The interactive role of the support was investigated and discussed. Among the tested samples, the sample with 30 wt.% Co (Co30/MPT) demonstrated superior performance in the OER. The reaction started at 1.65 V, and at 1.8 V, the current density reached 75 mA cm−2. The HER is most efficient on the sample containing 40 wt.% Ni (Ni40/MPT), where the current density reaches 95 mA at a potential of −0.5 V. The change in catalytic efficiency compared to that of the unsupported Ni and Co is due to synergism resulting from electronic interactions between the transition metal having a hyper-d-electron character and hypo-d-electron support. The pre-selected catalysts were integrated in membrane electrode assembly (MEA) using commercial and laboratory-prepared anion-conductive membranes and tested in a custom-made AEMEC. The performance was compared to that of MEA with a commercial carbon-supported Pt catalyst. It was found that the MEA with newly prepared catalysts demonstrated better performance in long-term operation (50 mA cm−2 at 1.8 V in a 60 h durability test), which, combined with the higher cost efficiency, gave credence to considering this combination of materials as promising for AEMEC applications. Full article
(This article belongs to the Special Issue Simulation-Aided Materials Design for Electrocatalysis)
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15 pages, 5807 KiB  
Article
Biodegradable Ca2+ Doped Mesoporous Silica Nanoparticles Promote Chemotherapy Synergism with Calcicoptosis and Activate Anti-Tumor Immunity
by Chao Liu, Xiaohui Tang and Gaofei Huang
Inorganics 2024, 12(6), 152; https://doi.org/10.3390/inorganics12060152 - 31 May 2024
Viewed by 241
Abstract
Mesoporous silica nanoparticles (MSNs), an excellent carrier material, have been widely used in tumor therapy as a vector for numerous therapeutic substances to boost therapeutical efficiency and specificity, such as loading them with chemotherapy drugs to improve the efficacy of chemotherapy. Nevertheless, they [...] Read more.
Mesoporous silica nanoparticles (MSNs), an excellent carrier material, have been widely used in tumor therapy as a vector for numerous therapeutic substances to boost therapeutical efficiency and specificity, such as loading them with chemotherapy drugs to improve the efficacy of chemotherapy. Nevertheless, they still face hurdles, such as lack of specificity and poor efficacy of monotherapy. The construction of multifunctional MSNs with excellent therapeutic effects by introducing metal ions has attracted the attention of many researchers. Herein, we demonstrated a calcium doped, chemotherapy drug doxorubicin (Dox) loaded, specific degradation nanoplatform, prepared using the sol–gel method by introducing calcium ions into an MSN framework, which enabled the doped nanoplatform to enhance chemotherapy and activate anti-tumor immune response. As a proof of concept, the doping of Ca2+ endowed MSNs with excellent specific degradation and pH responsive drug release, and enabled the synergy of chemotherapy and calcicoptosis. Furthermore, this nanoplatform also effectively elicited immunogenic cell death (ICD) and promoted the maturation of dendritic cells (DCs), realizing the activation of the anti-tumor immune system. The Ca2+ doped MSNs (CMSNs), that can activate immune response with specific degradation capability, demonstrate a practical strategy for the effective synergy between chemotherapy and calcicoptosis, providing a new paradigm for promoting chemotherapy-related treatment. Full article
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17 pages, 22331 KiB  
Article
Growth of KNbO3 Single Crystals by the Flux Method Using KBO2 as a Flux
by Thanh Trung Doan, John G. Fisher, Jong-Sook Lee, Huyen Tran Tran, Jie Gao, Jungwi Mok, Junseong Lee, Andreja Benčan, Goran Dražić, Syed Bilal Junaid and Jae-Hyeon Ko
Inorganics 2024, 12(6), 151; https://doi.org/10.3390/inorganics12060151 - 30 May 2024
Viewed by 329
Abstract
KNbO3 single crystals are grown by the self-flux method using K2CO3 as a flux, but often suffer from discolouration. In this work, KNbO3 single crystals were grown by the flux method using KBO2 as a flux. KNbO [...] Read more.
KNbO3 single crystals are grown by the self-flux method using K2CO3 as a flux, but often suffer from discolouration. In this work, KNbO3 single crystals were grown by the flux method using KBO2 as a flux. KNbO3 powder was prepared by the solid-state reaction of K2CO3 and Nb2O5. KBO2 was fabricated by the reaction of K2B4O7·4H2O and K2CO3. Single crystals of KNbO3 were grown in a Pt crucible and the structure and dielectric properties of the single crystals were investigated. X-ray diffraction showed the KNbO3 single crystals to have an orthorhombic Cmm2 perovskite unit cell at room temperature. The existence of ferroelastic domains was revealed by transmission electron microscopy. Electron probe microanalysis showed the single crystals to be stoichiometric and contain small amounts of B. Differential thermal analysis, Raman scattering and impedance spectroscopy were used to study the phase transitions. KBO2 may be a suitable flux for the growth of KNbO3 single crystals. Full article
(This article belongs to the Special Issue The State of the Art of Research on Perovskites Materials)
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9 pages, 1826 KiB  
Article
Effect of Synthesis Conditions on the Photoluminescent Properties of Si-Substituted CaYAlO4:Eu: Sources of Experimental Errors in Solid-State Synthesis
by Ju Hyun Oh, Yookyoung Lee, Jihee Kim, Woo Tae Hong, Hyun Kyoung Yang, Mijeong Kang and Seunghun Lee
Inorganics 2024, 12(6), 150; https://doi.org/10.3390/inorganics12060150 - 30 May 2024
Viewed by 291
Abstract
To improve the luminescent efficiency of and to design the color spectrum of phosphors, the comprehensive understanding of the correlation between physical parameters and luminescent properties is imperative, necessitating systematic experimental studies. However, unintentional variations across individually prepared samples impede the thorough investigation [...] Read more.
To improve the luminescent efficiency of and to design the color spectrum of phosphors, the comprehensive understanding of the correlation between physical parameters and luminescent properties is imperative, necessitating systematic experimental studies. However, unintentional variations across individually prepared samples impede the thorough investigation of the correlation. In this study, we investigate the possible sources of unintentional variation in the photoluminescence properties of phosphors during sample preparation using a solid-state reaction, explicitly focusing on the ball milling process. Based on the quantitative features of the photoluminescent properties and their associated statistical errors, we explore the impact of unintentional variation alongside intended systematic variation, highlighting its potential to obscure meaningful trends. Full article
(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials)
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11 pages, 4206 KiB  
Article
Discovering Novel Glass with Robust Crystallization Resistance via Amorphous Phase Separation Engineering
by Mou Deng, Mingzhong Wang, Yu Rao, Yinsheng Xu, Dong Wu, Shisheng Lin and Ping Lu
Inorganics 2024, 12(6), 149; https://doi.org/10.3390/inorganics12060149 - 29 May 2024
Viewed by 322
Abstract
Amorphous phase separation (APS) is ubiquitously found in a large number of glass systems, because the glass can be regarded as solid with a heterogeneous structure at the nanoscale. However, little attention has been paid to the big challenges in utilizing APS in [...] Read more.
Amorphous phase separation (APS) is ubiquitously found in a large number of glass systems, because the glass can be regarded as solid with a heterogeneous structure at the nanoscale. However, little attention has been paid to the big challenges in utilizing APS in searching novel amorphous glass from above to below, which highlights the meticulous microstructure tunability of glass. Correspondingly, we develop a novel SiO2-Al2O3-P2O5-Li2O-ZrO2 glass with APS (SAPLZ APS) which has robust crystallization resistance via the APS engineering. A comparative study is conducted to reveal the APS–crystallization property relationship. It can be found that the introduced APS can substantially impede the precipitated crystal growth in the studied glass system. Considering detailed glassy structure and microstructure, a diffusion barrier around each Li-rich droplet is created by the presence of P5+ concentration surrounding the Li-rich region. Meanwhile, due to the increase in Q4 at the expense of Q3, the polymerization degree in the Si-rich amorphous area can be enhanced, further increasing its viscosity and raising the kinetic barrier of Si-related crystal growth. These findings provide a new manner to develop new glass with superior anti-crystallization performance. Full article
(This article belongs to the Special Issue Recent Research and Application of Amorphous Materials)
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22 pages, 7390 KiB  
Article
Functionalization of Strontium Ferrite Nanoparticles with Novel Chitosan–Schiff Base Ligand for Efficient Removal of Pb(II) Ions from Aqueous Media
by Asma S. Al-Wasidi and Ehab A. Abdelrahman
Inorganics 2024, 12(6), 148; https://doi.org/10.3390/inorganics12060148 - 29 May 2024
Viewed by 285
Abstract
Lead contamination in water poses significant health risks, making its removal imperative. In this study, magnetic strontium ferrite (SrFe12O19) nanoparticles were facilely synthesized by the Pechini sol–gel method and subsequently functionalized with a novel chitosan–Schiff base ligand to obtain [...] Read more.
Lead contamination in water poses significant health risks, making its removal imperative. In this study, magnetic strontium ferrite (SrFe12O19) nanoparticles were facilely synthesized by the Pechini sol–gel method and subsequently functionalized with a novel chitosan–Schiff base ligand to obtain a novel inorganic/organic nanocomposite for removing Pb(II) ions from aqueous solutions. The chitosan–Schiff base ligand was synthesized through the reaction of chitosan with 2,4,5-trihydroxybenzaldehyde. The presence of two X-ray diffraction (XRD) peaks at 2Ɵ = 10.5° and 2Ɵ = 20.5°, alongside the characteristic SrFe12O19 peaks, confirmed the functionalization of the nanoparticles with the ligand. Additionally, a significant decrease in the saturation magnetization value from 40.29 emu/g in pure SrFe12O19 nanoparticles to 17.32 emu/g in the nanocomposite further verified the functionalization. The presence of carbon (C) and nitrogen (N) atoms in the energy-dispersive X-ray (EDX) pattern of the nanocomposite, in addition to iron (Fe), strontium (Sr), and oxygen (O), also confirmed the functionalization. The nanocomposite’s maximum adsorption capacity for Pb(II) ions was 390.63 mg/g. Moreover, the adsorption process is endothermic, spontaneous, and chemical, occurring via complexation with -C=N and -OH groups, and it fits well with the Langmuir equilibrium isotherm and the pseudo-second-order kinetic equation. Full article
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21 pages, 4844 KiB  
Article
Cyanide Addition to Diiron and Diruthenium Bis-Cyclopentadienyl Complexes with Bridging Hydrocarbyl Ligands
by Alessia Cinci, Gianluca Ciancaleoni, Stefano Zacchini and Fabio Marchetti
Inorganics 2024, 12(6), 147; https://doi.org/10.3390/inorganics12060147 - 28 May 2024
Viewed by 374
Abstract
We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu4NCN) of a series of dinuclear complexes based on the M2Cp2(CO)3 scaffold (M = Fe, Ru; Cp = η5 [...] Read more.
We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu4NCN) of a series of dinuclear complexes based on the M2Cp2(CO)3 scaffold (M = Fe, Ru; Cp = η5-C5H5), namely [M2Cp2(CO)2(µ-CO){µ,η12-CH=C=CMe2}]BF4 (1Fe-Ru), [Ru2Cp2(CO)2(µ-CO){µ,η12-C(Ph)=CHPh}]BF4 (2Ru) and [M2Cp2(CO)2(µ-CO){µ-CN(Me)(R)}]CF3SO3 (3Fe-Ru). While the reaction of 1Fe with Bu4NCN resulted in prevalent allenyl deprotonation, preliminary CO-NCMe substitution in 1Ru enabled cyanide addition to both the allenyl ligand (resulting in the formation of a h1:h2-allene derivative, 5A) and the two metal centers (affording 5B1 and 5B2). The mixture of 5B1-2 was rapidly converted into 5A in heptane solution at 100 °C, with 5A being isolated with a total yield of 60%. Following carbonyl-chloride substitution in 2Ru, CN was incorporated as a terminal ligand upon Cl displacement, to give the alkenyl complex 6 (84%). The reactivity of 3Fe and 3Ru is strongly influenced by both the metal element, M, and the aminocarbyne substituent, R. Thus, 7aRu was obtained with a 74% yield from cyanide attack on the carbyne in 3aRu (R = Cy, cyclohexyl), whereas the reaction involving the diiron counterpart 3aFe yielded an unclean mixture of the metastable 7aFe and the CO/CN substitution product 8aFe. The cyano-alkylidene complexes 7aRu (R = Cy) and 7bFe (R = Me) underwent CO loss and carbene to carbyne conversion in isopropanol at 60–80 °C, giving 8aRu (48%) and 8bFe (71%), respectively. The novel compounds 5A, 5B1-2, 6 and 7aRu were characterized by IR and NMR spectroscopy, with the structure of 7aRu further elucidated by single crystal X-ray diffraction analysis. Additionally, the DFT-optimized structures of potential isomers of 5A, 5B1-2 and 6 were calculated. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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14 pages, 3205 KiB  
Article
Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors
by Rieko Ishibashi, Ruka Koike, Yoriko Suda, Tatsuhiro Kojima, Toshiyuki Sumi, Toshiyuki Misawa, Kotaro Kizu, Yosuke Okamura and Takeru Ito
Inorganics 2024, 12(6), 146; https://doi.org/10.3390/inorganics12060146 - 23 May 2024
Viewed by 527
Abstract
Lanthanide elements such as europium exhibit distinctive emissions due to the transitions of inner-shell 4f electrons. Inorganic materials containing lanthanide elements have been widely used as phosphors in conventional displays. The hybridization of lanthanide ions with organic components enables to control of the [...] Read more.
Lanthanide elements such as europium exhibit distinctive emissions due to the transitions of inner-shell 4f electrons. Inorganic materials containing lanthanide elements have been widely used as phosphors in conventional displays. The hybridization of lanthanide ions with organic components enables to control of the material’s shapes and properties and broadens the possibility of lanthanide compounds as inorganic–organic materials. Lanthanide ion-containing polyoxometalate anions (Ln-POM) are a promising category as an inorganic component to design and synthesize inorganic–organic hybrids. Several inorganic–organic Ln-POM systems have been reported by hybridizing with cationic surfactants as luminescent materials. However, single-crystalline ordering has not been achieved in most cases. Here, we report syntheses and structures of inorganic–organic hybrid crystals of lanthanide-based POM and bolaamphiphile surfactants with two hydrophilic heads in one molecule. An emissive decatungstoeuropate ([EuW10O36]9−, EuW10) anion was employed as a lanthanide source. The bolaamphiphile counterparts are 1,8-octamethylenediammonium ([H3N(CH2)8NH3]2+, C8N2) and 1,10-decamethylenediammonium ([H3N(CH2)10NH3]2+, C10N2). Both hybrid crystals of C8N2-EuW10 and C10N2-EuW10 were successfully obtained as single crystals, and their crystal structures were unambiguously determined using X-ray diffraction measurements. The photoluminescence properties of C8N2-EuW10 and C10N2-EuW10 were investigated by means of steady-state and time-resolved spectroscopy. The characteristic emission derived from the EuW10 anion was retained after the hybridization process. Full article
(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials)
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