Inorganics

11 pages, 3062 KiB

Open AccessArticle

Controlling Chiral Self-Sorting in Truxene-Based Self-Assembled Cages

by Amina Benchohra, Simon Séjourné, Antoine Labrunie, Liam Miller, Enzo Charbonneau, Vincent Carré, Frédéric Aubriet, Magali Allain, Marc Sallé and Sébastien Goeb

Inorganics 2022, 10(7), 103; https://doi.org/10.3390/inorganics10070103 - 19 Jul 2022

Cited by 3 | Viewed by 2477

Abstract

Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M₂), afforded three chiral face-rotating stereoisomer polyhedra (M₆L₂). By tuning the length of the alkyl chains as well as the distance between both [...] Read more.

Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M₂), afforded three chiral face-rotating stereoisomer polyhedra (M₆L₂). By tuning the length of the alkyl chains as well as the distance between both ligands facing each other in the self-assemblies (M₆L₂), one can control the diastereomeric distribution between the expected homo- and hetero-chiral structures. Full article

(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)

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12 pages, 1769 KiB

Open AccessArticle

Copper (II)-Catalyzed Oxidation of Ascorbic Acid: Ionic Strength Effect and Analytical Use in Aqueous Solution

by Anastasia E. Murekhina, Daniil N. Yarullin, Maria A. Sovina, Pavel A. Kitaev and George A. Gamov

Inorganics 2022, 10(7), 102; https://doi.org/10.3390/inorganics10070102 - 18 Jul 2022

Cited by 13 | Viewed by 3059

Abstract

Copper is an important metal both in living organisms and in the industrial activity of humans, it is also a distributed water pollutant and a toxic agent capable of inducing acute and chronic health disorders. There are several fluorescent chemosensors for copper (II) [...] Read more.

Copper is an important metal both in living organisms and in the industrial activity of humans, it is also a distributed water pollutant and a toxic agent capable of inducing acute and chronic health disorders. There are several fluorescent chemosensors for copper (II) determination in solutions; however, they are often difficult to synthesize and solvent-sensitive, requiring a non-aqueous medium. The present paper improves the known analytical technique for copper (II) ions, where the linear dependence between the ascorbic acid oxidation rate constant and copper (II) concentration is used. The limits of detection and quantification of the copper (II) analysis kinetic method are determined to be 82 nM and 275 nM, respectively. In addition, the selectivity of the chosen indicator reaction is shown: Cu²⁺ cations can be quantified in the presence of the 5–20 fold excess of Co²⁺, Ni²⁺, and Zn²⁺ ions. The La³⁺, Ce³⁺, and UO₂²⁺ ions also do not catalyze the ascorbic acid oxidation reaction. The effect of the concentration of the common background electrolytes is studied, the anomalous influence for chloride-containing salts is observed and discussed. Full article

(This article belongs to the Section Organometallic Chemistry)

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12 pages, 1897 KiB

Open AccessArticle

Two-Photon Fluorescence in Red and Violet Conjugated Polymer Microspheres

by Yanyan Zhi, Ziwei Feng, Tanisha Mehreen, Xiaoyuan Liu, Kirsty Gardner, Xiangping Li, Bai-Ou Guan, Lijuan Zhang, Sergey I. Vagin, Bernhard Rieger and Alkiviathes Meldrum

Inorganics 2022, 10(7), 101; https://doi.org/10.3390/inorganics10070101 - 12 Jul 2022

Cited by 4 | Viewed by 2578

Abstract

We investigate the two-photon fluorescence (TPF) of conjugated polymer (CP) microspheres with diameters up to tens of micrometers. Two polymers, emitting in either the violet or red, were first synthesized and characterized in terms of their one-photon fluorescence and three-dimensional internal microstructure. Under [...] Read more.

We investigate the two-photon fluorescence (TPF) of conjugated polymer (CP) microspheres with diameters up to tens of micrometers. Two polymers, emitting in either the violet or red, were first synthesized and characterized in terms of their one-photon fluorescence and three-dimensional internal microstructure. Under femtosecond infrared excitation, both types of microspheres showed a strong TPF, which was investigated by the excitation intensity dependence, emission spectroscopy, time-resolved luminescence, and photobleaching dynamics. While the violet-fluorescent microspheres performed similarly compared to dye-doped polystyrene counterparts emitting at a similar wavelength, the red-fluorescent microspheres showed a two-orders-of-magnitude stronger TPF. This excellent performance is attributed to enhanced hyperpolarizability associated with intermolecular interactions in the polymer solid, indicating a route toward designed CP microspheres that could outperform currently-available microparticles for sensing or imaging applications involving two-photon fluorescence. Full article

(This article belongs to the Special Issue Colorimetric and Fluorescent Chemosensors for Metal Ions)

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8 pages, 604 KiB

Open AccessConcept Paper

Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B₂₀H₁₈]²⁻

by Varvara V. Avdeeva, Anna V. Vologzhanina, Alexey S. Kubasov, Nailya S. Akhmadullina, Oleg N. Shishilov, Elena A. Malinina and Nikolay T. Kuznetsov

Inorganics 2022, 10(7), 99; https://doi.org/10.3390/inorganics10070099 - 10 Jul 2022

Cited by 9 | Viewed by 1892

Abstract

Gold(III) complexation with the octadecahydrido-eicosaborate anion [B₂₀H₁₈]²⁻ was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl₂]BF₄ (L = bipy, phen) reacted with [B₂₀H₁₈]²⁻, complexes [...] Read more.

Gold(III) complexation with the octadecahydrido-eicosaborate anion [B₂₀H₁₈]²⁻ was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl₂]BF₄ (L = bipy, phen) reacted with [B₂₀H₁₈]²⁻, complexes [Au(L)Cl₂]₂[B₂₀H₁₈] were isolated. The compounds consisted of a cationic gold(III) complex [Au(L)Cl₂]⁺ and the hydridoborate cluster as a counterion. X-ray diffraction studies revealed weak B–H...Au interactions for both compounds. Note that more reactive anions [B_nH_n]²⁻ (n = 10, 12) in similar reactions with gold(III) complexes resulted in gold mirror reactions. Full article

(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

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17 pages, 3475 KiB

Open AccessArticle

Synthesis and Crystal Structures of Mn(II) and Co(II) Complexes as Catalysts for Oxidation of Cyclohexanone

by Adedibu C. Tella, Aaron Y. Isaac, Hadley S. Clayton, Adeniyi S. Ogunlaja, Aswathy T. Venugopalan, Marimuthu Prabu and Raja Thirumalaiswamy

Inorganics 2022, 10(7), 100; https://doi.org/10.3390/inorganics10070100 - 10 Jul 2022

Cited by 5 | Viewed by 2171

Abstract

The global demand on adipic usage in the production of plasticizers and synthetic polyamide is increasing. In line with the search for an efficient and energy-conserving way to isolate adipic acid (AA) in good yields, this paper introduces the oxidization of cyclohexanone utilizing [...] Read more.

The global demand on adipic usage in the production of plasticizers and synthetic polyamide is increasing. In line with the search for an efficient and energy-conserving way to isolate adipic acid (AA) in good yields, this paper introduces the oxidization of cyclohexanone utilizing two new coordination compounds, [Mn(2,6-pydc)₂](imi) (1) and [Co(H₂pza)₂(H₂O)₂(NO₃)].NO₃ (2), as catalysts. Compounds 1 and 2 were synthesized by room temperature and refluxing methods, and characterized by spectral analyses (IR and UV-Vis.), SEM, BET, TGA, elemental, and X-ray crystallography. The single crystal structure of compound 1 revealed that pyridinedicarboxylate (2,6-pydc) and imidazole (imi) moieties were coordinated to the Mn(II) atom through imine nitrogen and deprotonated oxygen atoms, to form an undistorted octahedral coordination geometry with the N₂O₄ donor set. The axial and equatorial planes containing O2, O4, O5, and O7 atoms were from two adjacent 2,6-pydc ligands which formed the unidendate donor ligand; imi, on the other hand, acted as a bidendate donor ligand. For compound 2, the Co(II) atom was being coordinated by two pyrazinamide (H₂pza) moieties, which acted as an unidendate donor ligand; two water molecules occupying the axial position, and one nitrate molecule occupying the apical position, were within the coordination sphere; a nitrate molecule was disordered outside the coordination sphere. The distance, 4.658 Å, between the Co1 atom and the N8 atom of the uncoordinated nitrate molecule, was within the range reported elsewhere. Cyclohexanone peroxidation experiments revealed that compound 1 exhibited unique catalytic performance by giving a 72.8% yield in adipic acid, in comparison to the 71.3% yield obtained with compound 2. The yields in AA were maintained by way of recyclability evaluation. The reaction kinetics of compound 2 gave less activation energy, E_a 2938 J mol⁻¹, while the thermodynamic parameters indicated that the chemical reactivity of cyclohexanone on the active surfaces of compounds 1 and 2 was via monolayer physisorption. Full article

(This article belongs to the Special Issue Metal-Organic Frameworks: A Diverse Class of Compounds with Structures and Applications Only Limited by the Imagination of the Researcher)

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13 pages, 1202 KiB

Open AccessArticle

Investigations on the Spin States of Two Mononuclear Iron(II) Complexes Based on N-Donor Tridentate Schiff Base Ligands Derived from Pyridine-2,6-Dicarboxaldehyde

by Yosef Bayeh, Nithin Suryadevara, Sören Schlittenhardt, Róbert Gyepes, Assefa Sergawie, Peter Hrobárik, Wolfgang Linert, Mario Ruben and Madhu Thomas

Inorganics 2022, 10(7), 98; https://doi.org/10.3390/inorganics10070098 - 8 Jul 2022

Cited by 3 | Viewed by 2543

Abstract

Iron(II)-Schiff base complexes are a well-studied class of spin-crossover (SCO) active species due to their ability to interconvert between a paramagnetic high spin-state (HS, S = 2, ⁵T₂) and a diamagnetic low spin-state (LS, S = 0, ¹A₁ [...] Read more.

Iron(II)-Schiff base complexes are a well-studied class of spin-crossover (SCO) active species due to their ability to interconvert between a paramagnetic high spin-state (HS, S = 2, ⁵T₂) and a diamagnetic low spin-state (LS, S = 0, ¹A₁) by external stimuli under an appropriate ligand field. We have synthesized two mononuclear Fe^II complexes, viz., [Fe(L¹)₂](ClO₄)₂.CH₃OH (1) and [Fe(L²)₂](ClO₄)₂.2CH₃CN (2), from two N₆–coordinating tridentate Schiff bases derived from 2,6-bis[(benzylimino)methyl]pyridine. The complexes have been characterized by elemental analysis, electrospray ionization–mass spectrometry (ESI-MS), Fourier-transform infrared spectroscopy (FTIR), solution state nuclear magnetic resonance spectroscopy, ¹H and ¹³C NMR (both theoretically and experimentally), single-crystal diffraction and magnetic susceptibility studies. The structural, spectroscopic and magnetic investigations revealed that 1 and 2 are with Fe–N₆ distorted octahedral coordination geometry and remain locked in LS state throughout the measured temperature range from 5–350 K. Full article

(This article belongs to the Special Issue Metal Complexes with N-donor Ligands)

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13 pages, 3637 KiB

Open AccessArticle

Nucleophilic Substitution at a Coordinatively Saturated Five-Membered NHC∙Haloborane Centre

by Gargi Kundu, Srinu Tothadi and Sakya S. Sen

Inorganics 2022, 10(7), 97; https://doi.org/10.3390/inorganics10070097 - 7 Jul 2022

Cited by 5 | Viewed by 2495

Abstract

In this paper, we have used a saturated five-membered N-Heterocyclic carbene (5SIDipp = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidine) for the synthesis of SNHC-haloboranes adducts and their further nucleophilic substitutions to put unusual functional groups at the central boron atom. The reaction of 5-SIDipp with RBCl₂ yields [...] Read more.

In this paper, we have used a saturated five-membered N-Heterocyclic carbene (5SIDipp = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidine) for the synthesis of SNHC-haloboranes adducts and their further nucleophilic substitutions to put unusual functional groups at the central boron atom. The reaction of 5-SIDipp with RBCl₂ yields Lewis-base adducts, 5-SIDipp·RBCl₂ [R = H (1), Ph (2)]. The hydrolysis of 1 gives the NHC stabilized boric acid, 5-SIDipp·B(OH)₃ (3), selectively. Replacement of chlorine atoms from 1 and 2 with one equivalent of AgOTf led to the formation of 5-SIDipp·HBCl(OTf) (4) and 5-SIDipp·PhBCl(OTf) (5a), where all the substituents on the boron atoms are different. The addition of two equivalents of AgNO₃ to 2 leads to the formation of rare di-nitro substituted 5-SIDipp·BPh(NO₃)₂ (6). Further, the reaction of 5-SIDipp with B(C₆F₅)₃ in tetrahydrofuran and diethyl ether shows a frustrated Lewis pair type small molecule activated products, 7 and 8. Full article

(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

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12 pages, 4393 KiB

Open AccessArticle

Rearrangement of Diferrocenyl 3,4-Thiophene Dicarboxylate

by Asma Ghazzy, Deeb Taher, Marcus Korb, Khaled Al Khalyfeh, Wissam Helal, Hazem Amarne, Tobias Rüffer, Zakariyya Ishtaiwi and Heinrich Lang

Inorganics 2022, 10(7), 96; https://doi.org/10.3390/inorganics10070096 - 6 Jul 2022

Cited by 6 | Viewed by 1837

Abstract

Treatment of 3,4-(ClC(O))₂-^cC₄H₂S (1) with [FcCH₂OLi] (2-Li) (Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₄)) in a 1:2 ratio gave 3,4-(FcCH₂ [...] Read more.

Treatment of 3,4-(ClC(O))₂-^cC₄H₂S (1) with [FcCH₂OLi] (2-Li) (Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₄)) in a 1:2 ratio gave 3,4-(FcCH₂OC(O))₂-^cC₄H₂S (3). Compound 3 decomposes in solution during crystallization to produce FcCH₂OH (2) along with 3,4-thiophenedicarboxylic anhydride (4). The cyclic voltammogram of 3 exhibits a reversible ferrocene-related redox couple (E_1/₂ = 108 mV, vs. Cp₂Fe/Cp₂Fe⁺) using [NⁿBu₄] [B(C₆F₅)₄] as the supporting electrolyte. DFT calculations reveal that the energy values of the LUMO orbitals of 3 (3,4-thiophene core) show 1 eV higher energies than that one of 2,5-(FcCH₂OC(O))₂-^cC₄H₂S (5), both compounds’ HOMO orbitals are close to each other. Compound 4 was characterized by single X-ray structure analysis. It forms a band-type structure based on intermolecular O1···S1 interactions being parallel to (110) and (1–10) in the solid state, while electrostatic C···O interactions between the C=O functionalities of adjacent molecules connect both 3D-networks. Hirshfeld surface analysis was used to gain more insight into the intermolecular interactions in 4, the enrichment ratios (E) suggest that O···H, S···S, and O···C are the most favored intermolecular interactions, as shown by E values above 1.20. The relevance of the weak O···H, O···O, and O···C contacts in stabilizing the molecular structure of 4 was highlighted by the interaction energies between molecular pairs. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

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17 pages, 2171 KiB

Open AccessArticle

Chloride Binding Properties of a Macrocyclic Receptor Equipped with an Acetylide Gold(I) Complex: Synthesis, Characterization, Reactivity, and Cytotoxicity Studies

by Andrea Rivoli, Gemma Aragay, María Concepción Gimeno and Pablo Ballester

Inorganics 2022, 10(7), 95; https://doi.org/10.3390/inorganics10070095 - 5 Jul 2022

Cited by 3 | Viewed by 2383

Abstract

In this work, we report the synthesis and characterization of a mono-nuclear “two wall” aryl-extended calix[4]pyrrole receptor (2Au) decorated with an acetylide-gold(I)-PTA complex at its upper rim. We describe the ¹H NMR titration experiments of 2Au and its “two wall” [...] Read more.

In this work, we report the synthesis and characterization of a mono-nuclear “two wall” aryl-extended calix[4]pyrrole receptor (2Au) decorated with an acetylide-gold(I)-PTA complex at its upper rim. We describe the ¹H NMR titration experiments of 2Au and its “two wall” aryl-extended calix[4]pyrrole synthetic precursors: the non-symmetric mono-iodo-mono-ethynyl 2 and the symmetric bis-iodo 3 with TBACl in dichloromethane and acetone solution. In acetone solution, we use isothermal titration calorimetry (ITC) experiments to thermodynamically characterize the formed 1:1 chloride complexes and perform pair-wise competitive binding experiments. In both solvents, we measured a decrease in the binding constant of the mono-nuclear 2Au complex for chloride compared to the parent mono-iodo-mono-ethynyl 2. In turn, receptor 2 also shows a reduction in binding affinity for chloride compared to its precursor bis-iodo calix[4]pyrrole 3. The free energy differences (∆G) of the 1:1 chloride complexes cannot be exclusively attributed to their dissimilar electrostatic surface potential values either at the center of the meso-phenyl wall or its para-substituent. We conclude that solvation/desolvation processes play an important role in the stabilization of the chloride complexes. In acetone solution and in the presence of TBACl, 6Au, a reference compound for the acetylide Au(I)•PTA unit, produces a bis(alkynyl)gold(I) anionic complex [7Au]⁻. Thus, the observation of two separate sets of signals for the bound aromatic calix[4]pyrrole protons, when more than 1 equiv. of the salt is added, is assigned to the formation of the chloride complexes of 2Au and of the “in situ” formed calix[4]pyrrole anionic dimer [8Au]⁻. Finally, preliminary data obtained in cell viability assays of 2Au and 6Au with human cancer cells lines assign them with moderate activities showing that the calix[4]pyrrole unit is not relevant. Full article

(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)

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13 pages, 3762 KiB

Open AccessArticle

Temperature-Sensitive Chameleon Luminescent Films Based on PMMA Doped with Europium(III) and Terbium(III) Anisometric Complexes

by Yuriy G. Galyametdinov, Aleksandr S. Krupin and Andrey A. Knyazev

Inorganics 2022, 10(7), 94; https://doi.org/10.3390/inorganics10070094 - 4 Jul 2022

Cited by 15 | Viewed by 2629

Abstract

The spin-coating technique was used to produce composite films consisting of PMMA polymer doped with anisometric complexes of Eu(III) and Tb(III). It was found that an increase in the content of Tb³⁺ complexes intensifies emission of both ions due to the intermolecular [...] Read more.

The spin-coating technique was used to produce composite films consisting of PMMA polymer doped with anisometric complexes of Eu(III) and Tb(III). It was found that an increase in the content of Tb³⁺ complexes intensifies emission of both ions due to the intermolecular energy transfer from the Tb(III) complex to the Eu(III) complex, which results in the increase in the relative luminescence quantum yield of Eu(III) ion by 36%. The temperature sensitivity of the film luminescence intensity and lifetime in the range of 296–363 K was investigated. The maximum relative sensitivity of the films reaches 5.44% × K⁻¹ and exceeds that of all known lanthanide-containing thermal sensors designed for measuring physiological temperatures. In combination with changing luminescence color, such a sensitivity makes these films promising colorimetric thermal sensors for in situ temperature measurements. Full article

(This article belongs to the Special Issue Light Emitting Metal Complexes)

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12 pages, 4598 KiB

Open AccessArticle

Purification and Characterization of High Purity Nano Zirconia by Liquid-Liquid Extraction Using D2EHPA/p-Xylenes

by Manh Nhuong Chu, Mai Xuan Truong, Thi Hien Lan Nguyen, Tra Huong Do, Thi Tu Anh Duong, Thi Kim Ngan Tran, Thi Cam Quyen Ngo, Thi To Loan Nguyen, Thi Hau Vu and Mai An Pham

Inorganics 2022, 10(7), 93; https://doi.org/10.3390/inorganics10070093 - 1 Jul 2022

Cited by 4 | Viewed by 2300

Abstract

In this paper, Zr(IV) nitrate solution decomposed from Viet Nam zircon concentrate was the source of zirconium extraction by liquid-liquid extraction (L.L.E). The FT-IR and UV-Vis spectra confirmed the extraction of Zr(IV) by D2EHPA/p-xylenes. There were four stages for the purification of impurities [...] Read more.

In this paper, Zr(IV) nitrate solution decomposed from Viet Nam zircon concentrate was the source of zirconium extraction by liquid-liquid extraction (L.L.E). The FT-IR and UV-Vis spectra confirmed the extraction of Zr(IV) by D2EHPA/p-xylenes. There were four stages for the purification of impurities from the Zr matrix. First, the extraction of elements in 3.0 M HNO₃ by 50% D2EHPA/p-xylenes was conducted. Second, two scrubbing cycles of impurities using 6.0 M HNO₃, 76.5% of the total amount of Zr(IV) were retained in the organic phase, and 23.5% remained in the aqueous phase. Third, the stripping of a macro amount of zirconium from loaded D2EHPA has been effectively carried out using 1.5 M H₂SO₄ with a stripping efficiency of 99.6%. Fourth, concentrated ammonia was added to the solution Zr(IV) after stripping extraction to form precipitate for calcination at 550 °C for the final products. The refined products were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), EDS, XRF, and diffuse reflectance spectroscopy. The ZrO₂ has high purity, is nanospherical, and has a uniform sphere-like morphology with small grain size of less than 30 nm and a bandgap value of about 3.30 eV. Full article

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14 pages, 2780 KiB

Open AccessArticle

Electrochemical Redox In-Situ Welding of Silver Nanowire Films with High Transparency and Conductivity

by Wang Zhang, Jiashuan Bao, Chenhui Xu, Pengfeng Zhu, Xiangliang Pan and Rui Li

Inorganics 2022, 10(7), 92; https://doi.org/10.3390/inorganics10070092 - 30 Jun 2022

Cited by 1 | Viewed by 2393

Abstract

Silver nanowire (AgNW) networks with high transparency and conductivity are crucial to developing transparent conductive films (TCFs) for flexible optoelectronic devices. However, AgNW-based TCFs still suffer from the high contact resistance of AgNW junctions with both the in-plane and out-of-plane charge transport barrier. [...] Read more.

Silver nanowire (AgNW) networks with high transparency and conductivity are crucial to developing transparent conductive films (TCFs) for flexible optoelectronic devices. However, AgNW-based TCFs still suffer from the high contact resistance of AgNW junctions with both the in-plane and out-of-plane charge transport barrier. Herein, we report a rapid and green electrochemical redox strategy to in-situ weld AgNW networks for the enhanced conductivity and mechanical durability of TCFs with constant transparency. The welded TCFs show a marked decrease of the sheet resistance (reduced to 45.5% of initial values on average) with high transmittance of 97.02% at 550 nm (deducting the background of substrates). The electrochemical welding treatment enables the removal of the residual polyvinylpyrrolidone layer and the in-situ formation of Ag solder in the oxidation and reduction processes, respectively. Furthermore, local conductivity studies confirm the improvement of both the in-plane and the out-of-plane charge transport by conductive atomic force microscopy. This proposed electrochemical redox method provides new insights on the welding of AgNW-based TCFs with high transparency and low resistance for the development of next-generation flexible optoelectronic devices. Furthermore, such conductive films based on the interconnected AgNW networks can be acted as an ideal supporter to construct heterogeneous structures with other functional materials for wide applications in photocatalysis and electrocatalysis. Full article

(This article belongs to the Special Issue Metal Nanomaterials as Efficient Electrocatalysts)

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8 pages, 7056 KiB

Open AccessCommunication

Magnetocaloric Effect of Two Gd-Based Frameworks

by Bo-Liang Liu, Qiao-Fei Xu, La-Sheng Long and Lan-Sun Zheng

Inorganics 2022, 10(7), 91; https://doi.org/10.3390/inorganics10070091 - 25 Jun 2022

Cited by 1 | Viewed by 2287

Abstract

Magnetic refrigeration material is the key to adiabatic demagnetization refrigeration technology. In this work, two magnetic refrigerants, Gd₅(C₄O₄)(HCOO)₃(CO₃)₂(OH)₆·2.5H₂O (1) and Gd₂(OH)₄SO [...] Read more.

Magnetic refrigeration material is the key to adiabatic demagnetization refrigeration technology. In this work, two magnetic refrigerants, Gd₅(C₄O₄)(HCOO)₃(CO₃)₂(OH)₆·2.5H₂O (1) and Gd₂(OH)₄SO₄ (2), were prepared through hydrothermal reaction. Magnetic study reveals that their magnetic entropy changes are 24.8 J kg⁻¹ K⁻¹ for 1 and 15.1 J kg⁻¹ K⁻¹ for 2 at 2 K and 2 T, respectively. The magnetic entropy changes of 1 and 2 at T = 2 K and ∆H = 2 T exceed most gadolinium hydroxyl compounds, indicating that magnetic refrigerants with large magnetic entropy changes at low magnetic fields can be obtained by introducing more weak magnetic exchange ligands to replace hydroxyl groups in gadolinium hydroxyl compounds. Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Lanthanide and Actinide Molecular Compounds)

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17 pages, 3527 KiB

Open AccessArticle

Synthesis, Structures and Chemical Reactivity of Dithiolato-Bridged Ni-Fe Complexes as Biomimetics for the Active Site of [NiFe]-Hydrogenases

by Li-Cheng Song, Shuai Chen, Xiao-Feng Han, Zhen-Qing Zhang, Yin-Peng Wang and Yi-Xiong Dong

Inorganics 2022, 10(7), 90; https://doi.org/10.3390/inorganics10070090 - 24 Jun 2022

Cited by 2 | Viewed by 1843

Abstract

To develop the structural and functional modeling chemistry of [NiFe]-H₂ases, we have carried out a study regarding the synthesis, structural characterization and reactivity of a new series of [NiFe]-H₂ase model complexes. Thus, treatment of diphosphine dppb-chelated Ni complex (dppb)NiCl [...] Read more.

To develop the structural and functional modeling chemistry of [NiFe]-H₂ases, we have carried out a study regarding the synthesis, structural characterization and reactivity of a new series of [NiFe]-H₂ase model complexes. Thus, treatment of diphosphine dppb-chelated Ni complex (dppb)NiCl₂ (dppb = 1,2-(Ph₂P)₂C₆H₄) with (dppv)Fe(CO)₂(pdt) (dppv = 1,2-(Ph₂P)₂C₂H₂, pdt = 1,3-propanedithiolate) and NaBF₄ gave dicarbonyl complex [(dppb)Ni(pdt)Fe(CO)₂(dppv)](BF₄)₂ ([A](BF₄)₂). Further treatment of [A](BF₄)₂ with Me₃NO and Bu₄NCN or KSCN afforded t-cyanido and t-isothiocyanato complexes [(dppb)Ni(pdt)Fe(CO)(t-R)(dppv)]BF₄ ([1]BF₄, R = CN; [2]BF₄, R = NCS), respectively. While azadiphosphine MeN(CH₂PPh₂)₂-chelated t-hydride complex [MeN(CH₂PPh₂)₂Ni(pdt)Fe(CO)(t-H)(dppv)]BF₄ ([3]BF₄) was prepared by treatment of dicarbonyl complex [MeN(CH₂PPh₂)₂Ni(pdt)Fe(CO)₂(dppv)](BF₄)₂ ([B](BF₄)₂) with Me₃NO and 1.5 MPa of H₂, treatment of dicarbonyl complex [B](BF₄)₂ with Me₃NO (without H₂) in pyridine resulted in formation of a novel monocarbonyl complex [MeN(CH₂PPh₂)₂Ni(SCHCH₂CH₂S)Fe(CO)(dppv)]BF₄ ([4]BF₄) via the unexpected sp³ C-H bond activation reaction. Furthermore, azadiphosphine PhN(CH₂PPh₂)₂-chelated µ-mercapto complex [PhN(CH₂PPh₂)₂Ni(pdt)Fe(CO)(µ-SH)(dppv)]BF₄ ([5]BF₄) was prepared by treatment of dicarbonyl complex [PhN(CH₂PPh₂)₂Ni(pdt)Fe(CO)₂(dppv)](BF₄)₂ ([C](BF₄)₂) with Me₃NO and H₂S gas, whereas treatment of azadiphosphine Ph₂CHN(CH₂PPh₂)₂-chelated dicarbonyl complex [Ph₂CHN(CH₂PPh₂)₂Ni(pdt)Fe(CO)₂(dppe)](BF₄)₂ ([D](BF₄)₂, dppe = 1,2-(Ph₂P)₂C₂H₄) with Me₃NO⋅2H₂O gave rise to µ-hydroxo complex [Ph₂CHN(CH₂PPh₂)₂Ni(pdt)Fe(CO)(µ-OH)(dppe)]BF₄ ([6]BF₄). All the possible pathways for formation of the new model complexes are briefly discussed, and their structures were fully characterized by various spectroscopic techniques and for six of them by X-ray crystallography. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

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14 pages, 5308 KiB

Open AccessArticle

Enhanced Photocatalytic Degradation of Rhodamine-B under Led Light Using CuZnAl Hydrotalcite Synthesized by Co-Precipitation Technique

by Van Nhuong Vu, Thi Ha Thanh Pham, Maiboun Chanthavong, Tra Huong Do, Thi Hien Lan Nguyen, Quoc Dung Nguyen and Thi Kim Ngan Tran

Inorganics 2022, 10(7), 89; https://doi.org/10.3390/inorganics10070089 - 23 Jun 2022

Cited by 7 | Viewed by 2389

Abstract

The co-precipitation method was employed to synthesize a set of ZnAl hydrotalcite materials modified by Cu²⁺. The synthesized materials have a similar lamellar structure to that of hydrotalcite. The distance between layers is in the range of 7.73–8.56 Å. The network [...] Read more.

The co-precipitation method was employed to synthesize a set of ZnAl hydrotalcite materials modified by Cu²⁺. The synthesized materials have a similar lamellar structure to that of hydrotalcite. The distance between layers is in the range of 7.73–8.56 Å. The network parameters a and c ranged from 3.058 to 3.074 Å and from 23.01 to 24.44, respectively. According to the IUPAC classification, the composites possess a mesoporous structure which belongs to class IV, type H 3. Particularly, the absorption edge shifts strongly to the visible light region when increasing the molar ratio of Cu²⁺ in the samples from 0 to 3.5. The photocatalytic activity of the synthetic materials was evaluated through the degradation efficiency of rhodamine-B (Rh-B) in the water and colorants in textile wastewater. The present study was the first to synthesize a material sample that contains a molar ratio of Cu²⁺ in the range of 2.5–3.5 and has high catalytic activities. They were able to degrade Rh-B at a high concentration (100 ppm) with a conversion rate of approximately 90% after 240 min of irradiation using a 30 W LED light. The catalytic activity of the composites depends on the molar ratio of modified Cu²⁺, the value of environmental pH, the H₂O₂ concentration and the irradiation time. Full article

(This article belongs to the Special Issue Inorganic Compounds for Catalysis)

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18 pages, 5928 KiB

Open AccessReview

Anthracene-Containing Metallacycles and Metallacages: Structures, Properties, and Applications

by Jian-Hong Tang and Yu-Wu Zhong

Inorganics 2022, 10(7), 88; https://doi.org/10.3390/inorganics10070088 - 22 Jun 2022

Cited by 5 | Viewed by 3160

Abstract

Due to its highly conjugated panel-like structure and unique photophysical and chemical features, anthracene has been widely used for fabricating attractive and functional supramolecular assemblies, including two-dimensional metallacycles and three-dimensional metallacages. The embedded anthracenes in these assemblies often show synergistic effects on enhancing [...] Read more.

Due to its highly conjugated panel-like structure and unique photophysical and chemical features, anthracene has been widely used for fabricating attractive and functional supramolecular assemblies, including two-dimensional metallacycles and three-dimensional metallacages. The embedded anthracenes in these assemblies often show synergistic effects on enhancing the desired supramolecular and luminescent properties. This review focuses on the metallasupramolecular architectures with anthracene-containing building blocks, as well as their applications in host-guest chemistry, stimulus response, molecular sensing, light harvesting, and biomedical science. Full article

(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)

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14 pages, 3430 KiB

Open AccessArticle

Synthesis of Hierarchically Ordered Porous Silica Materials for CO₂ Capture: The Role of Pore Structure and Functionalized Amine

by Xiaoqi Jin, Jinlong Ge, Liyuan Zhang, Zhong Wu, Linlin Zhu and Mingwen Xiong

Inorganics 2022, 10(7), 87; https://doi.org/10.3390/inorganics10070087 - 21 Jun 2022

Cited by 8 | Viewed by 2333

Abstract

Hierarchically ordered porous silica materials (HSMs) with a micro/mesoporous structure were successfully prepared with the sol-gel method using dextran, dextran/CTAB, and CTAB as templates. The obtained hierarchically structured silica was successfully modified with amine groups through post-grafting and one-pot methods. Their architectural features [...] Read more.

Hierarchically ordered porous silica materials (HSMs) with a micro/mesoporous structure were successfully prepared with the sol-gel method using dextran, dextran/CTAB, and CTAB as templates. The obtained hierarchically structured silica was successfully modified with amine groups through post-grafting and one-pot methods. Their architectural features and texture parameters were characterized by XRD, N₂ adsorption–desorption isotherms, SEM, TEM, FTIR, and TGA techniques. The results demonstrated that the pore structure depended on the reaction temperature and the amount of CTAB added in the synthesis procedure. A series of porous silica with hierarchical pore structures possessed abundant micropores, ordered mesopores, and a tunable surface area and pore volume. After modification, the ordered structure of the hierarchical porous silica almost disappeared due to the presence of amine groups in the pore channel. Furthermore, to explore the effect of pore structures and amine groups on CO₂ adsorption performance, before and after amine modification of HSMs, adsorbents were evaluated regarding the capacity of collecting CO₂ for comparison. According to these results, the varying microporous content, pore size distribution, and density of the amine groups were important factors determining the capacity of CO₂ capture. Full article

(This article belongs to the Section Inorganic Materials)

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Inorganics, Volume 10, Issue 7 (July 2022) – 17 articles

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