Next Issue
Volume 10, August
Previous Issue
Volume 10, June
 
 

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

Cover Story (view full-size image): A mono-nuclear “two wall” aryl-extended caxli[4]pyrrole receptor decorated with an acetylide–gold(I)–PTA complex at its upper rim is synthesized. The binding properties of the unprecedented receptor and their synthetic precursors (R= I and ethynyl) towards chloride are studied in dichloromethane and acetone. The calculated ESP values at the centers of the aromatic ring and at the para‐substituent (R) of the differently substituted aromatic walls were not enough to explain the dissimilar free energies of binding of the 1:1 chloride complexes exclusively in terms of repulsive anion–π interactions. The calix[4]pyrrole acetylide gold(I) receptor binds chloride exclusively in the cone conformation, and the presence of free chloride in solution induces the formation of a gold(I)–anionic calix[4]pyrrole dimer. View this paper
  • Issues are regarded as officially published after their release is announced to the table of contents alert mailing list.
  • You may sign up for e-mail alerts to receive table of contents of newly released issues.
  • PDF is the official format for papers published in both, html and pdf forms. To view the papers in pdf format, click on the "PDF Full-text" link, and use the free Adobe Reader to open them.
Order results
Result details
Section
Select all
Export citation of selected articles as:
11 pages, 3062 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070103 - 19 Jul 2022
Cited by 3 | Viewed by 1832
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)
Show Figures

Graphical abstract

12 pages, 1769 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070102 - 18 Jul 2022
Cited by 10 | Viewed by 1992
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)
Show Figures

Figure 1

12 pages, 1897 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070101 - 12 Jul 2022
Cited by 3 | Viewed by 1922
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)
Show Figures

Graphical abstract

8 pages, 604 KiB  
Concept 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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070099 - 10 Jul 2022
Cited by 5 | Viewed by 1512
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 [BnHn]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)
Show Figures

Graphical abstract

17 pages, 3475 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070100 - 10 Jul 2022
Cited by 3 | Viewed by 1593
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, Ea 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
Show Figures

Figure 1

13 pages, 1202 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070098 - 08 Jul 2022
Cited by 1 | Viewed by 1965
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 FeII 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)
Show Figures

Figure 1

13 pages, 3637 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070097 - 07 Jul 2022
Cited by 3 | Viewed by 1960
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)
Show Figures

Graphical abstract

12 pages, 4393 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070096 - 06 Jul 2022
Cited by 3 | Viewed by 1446
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 (E1/2 = 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)
Show Figures

Figure 1

17 pages, 2171 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070095 - 05 Jul 2022
Cited by 3 | Viewed by 1868
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)
Show Figures

Figure 1

13 pages, 3762 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070094 - 04 Jul 2022
Cited by 10 | Viewed by 2043
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)
Show Figures

Graphical abstract

12 pages, 4598 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070093 - 01 Jul 2022
Cited by 3 | Viewed by 1795
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
Show Figures

Figure 1

14 pages, 2780 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070092 - 30 Jun 2022
Cited by 1 | Viewed by 1750
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)
Show Figures

Figure 1

8 pages, 7056 KiB  
Communication
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070091 - 25 Jun 2022
Cited by 1 | Viewed by 1583
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
Show Figures

Figure 1

17 pages, 3527 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070090 - 24 Jun 2022
Cited by 1 | Viewed by 1455
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)
Show Figures

Figure 1

14 pages, 5308 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070089 - 23 Jun 2022
Cited by 6 | Viewed by 1855
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)
Show Figures

Figure 1

18 pages, 5928 KiB  
Review
Anthracene-Containing Metallacycles and Metallacages: Structures, Properties, and Applications
by Jian-Hong Tang and Yu-Wu Zhong
Inorganics 2022, 10(7), 88; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070088 - 22 Jun 2022
Cited by 5 | Viewed by 2222
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)
Show Figures

Figure 1

14 pages, 3430 KiB  
Article
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://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10070087 - 21 Jun 2022
Cited by 5 | Viewed by 1688
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)
Show Figures

Figure 1

Previous Issue
Next Issue
Back to TopTop