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Showing 1 - 36 of 36 Journals sorted alphabetically
Acta Polymerica     Hybrid Journal   (Followers: 10)
Additives for Polymers     Full-text available via subscription   (Followers: 22)
Advances in Inorganic Chemistry     Full-text available via subscription   (Followers: 14)
Advances in Polymer Technology     Open Access   (Followers: 15)
Bioinorganic Chemistry and Applications     Open Access   (Followers: 11)
Comments on Inorganic Chemistry: A Journal of Critical Discussion of the Current Literature     Hybrid Journal   (Followers: 2)
Communication in Inorganic Synthesis     Open Access  
Current Inorganic Chemistry     Hybrid Journal  
European Journal of Inorganic Chemistry     Hybrid Journal   (Followers: 14)
European Polymer Journal     Hybrid Journal   (Followers: 46)
High Performance Polymers     Hybrid Journal   (Followers: 1)
Indian Journal of Chemistry - Section A     Open Access   (Followers: 8)
Inorganic and Nano-Metal Chemistry     Hybrid Journal  
Inorganic Chemistry     Hybrid Journal   (Followers: 40)
Inorganic Chemistry Communications     Hybrid Journal   (Followers: 15)
Inorganic Materials     Hybrid Journal   (Followers: 6)
Inorganic Materials: Applied Research     Hybrid Journal   (Followers: 1)
Inorganica Chimica Acta     Hybrid Journal   (Followers: 10)
Inorganics     Open Access   (Followers: 3)
International Journal of Bio-Inorganic Hybrid Nanomaterials     Open Access   (Followers: 2)
International Journal of Inorganic Chemistry     Open Access   (Followers: 4)
JBIC Journal of Biological Inorganic Chemistry     Hybrid Journal   (Followers: 4)
Journal of Inorganic and Organometallic Polymers and Materials     Hybrid Journal   (Followers: 11)
Journal of Inorganic Biochemistry     Hybrid Journal   (Followers: 5)
Journal of Inorganic Chemistry     Open Access   (Followers: 4)
Journal of Polymers and the Environment     Hybrid Journal   (Followers: 1)
Journal of Progressive Research in Chemistry     Open Access   (Followers: 8)
Journal of Separation Science     Hybrid Journal   (Followers: 10)
Materials Today Chemistry     Hybrid Journal   (Followers: 2)
Open Journal of Inorganic Chemistry     Open Access   (Followers: 3)
Plasmas and Polymers     Hybrid Journal  
Polymer Bulletin     Hybrid Journal   (Followers: 9)
Polymer Composites     Hybrid Journal   (Followers: 19)
Russian Journal of Inorganic Chemistry     Hybrid Journal   (Followers: 2)
Separation Science plus (SSC plus)     Hybrid Journal  
Zeitschrift für anorganische und allgemeine Chemie     Hybrid Journal   (Followers: 2)
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Number of Followers: 3  

  This is an Open Access Journal Open Access journal
ISSN (Online) 2304-6740
Published by MDPI Homepage  [240 journals]
  • Inorganics, Vol. 9, Pages 66: Study of DNA Interaction and Cytotoxicity

    • Authors: Gurunath Sahu, Edward R. T. Tiekink, Rupam Dinda
      First page: 66
      Abstract: Two new oxidovanadium(V) complexes, (HNEt3)[VVO2L] (1) and [(VVOL)2μ-O] (2), have been synthesized using a tridentate Schiff base ligand H2L [where H2L = 4-((E)-(2-hydroxy-5-nitrophenylimino)methyl)benzene-1,3-diol] and VO(acac)2 as starting metal precursor. The ligand and corresponding metal complexes are characterized by physicochemical (elemental analysis), spectroscopic (FT-IR, UV–Vis, and NMR), and spectrometric (ESI–MS) methods. X-ray crystallographic analysis indicates the anion in salt 1 features a distorted square-pyramidal geometry for the vanadium(V) center defined by imine-N, two phenoxide-O, and two oxido-O atoms. The interaction of the compounds with CT–DNA was studied through UV–Vis absorption titration and circular dichroism methods. The results indicated that complexes showed enhanced binding affinity towards DNA compared to the ligand molecule. Finally, the in vitro cytotoxicity studies of H2L, 1, and 2 were evaluated against colon cancer (HT-29) and mouse embryonic fibroblast (NIH-3T3) cell lines by MTT assay. The results demonstrated that the compounds manifested a cytotoxic potential comparable with clinically referred drugs and caused cell death by apoptosis.
      Citation: Inorganics
      PubDate: 2021-08-27
      DOI: 10.3390/inorganics9090066
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 67: 2-Aminopyrimidinium Decavanadate:
           Experimental and Theoretical Characterization, Molecular Docking, and
           Potential Antineoplastic Activity

    • Authors: Amalia García-García, Lisset Noriega, Francisco J. Meléndez-Bustamante, María Eugenia Castro, Brenda L. Sánchez-Gaytán, Duane Choquesillo-Lazarte, Enrique González-Vergara, Antonio Rodríguez-Diéguez
      First page: 67
      Abstract: The interest in decavanadate anions has increased in recent decades, since these clusters show interesting applications as varied as sensors, batteries, catalysts, or new drugs in medicine. Due to the capacity of the interaction of decavanadate with a variety of biological molecules because of its high negative charge and oxygen-rich surface, this cluster is being widely studied both in vitro and in vivo as a treatment for several global health problems such as diabetes mellitus, cancer, and Alzheimer’s disease. Here, we report a new decavanadate compound with organic molecules synthesized in an aqueous solution and structurally characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. The decavanadate anion was combined with 2-aminopyrimidine to form the compound [2-ampymH]6[V10O28]·5H2O (1). In the crystal lattice, organic molecules are stacked by π–π interactions, with a centroid-to-centroid distance similar to that shown in DNA or RNA molecules. Furthermore, computational DFT calculations of Compound 1 corroborate the hydrogen bond interaction between pyrimidine molecules and decavanadate anions, as well as the π–π stacking interactions between the central pyrimidine molecules. Finally, docking studies with test RNA molecules indicate that they could serve as other potential targets for the anticancer activity of decavanadate anion.
      Citation: Inorganics
      PubDate: 2021-08-30
      DOI: 10.3390/inorganics9090067
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 68: Oxidoborates Templated by Cationic
           Nickel(II) Complexes and Self-Assembled from B(OH)3

    • Authors: Mohammed A. Altahan, Michael A. Beckett, Simon J. Coles, Peter N. Horton
      First page: 68
      Abstract: Several oxidoborates, self-assembled from B(OH)3 and templated by cationic Ni(II) coordination compounds, were synthesized by crystallization from aqueous solution. These include the ionic compounds trans-[Ni(NH3)4(H2O)2][B4O5(OH)4].H2O (1), s-[Ni(dien)2][B5O6(OH)4]2 (dien = N-(2-aminoethyl)-1,2-ethanediamine (2), trans-[Ni(dmen)2(H2O)2] [B5O6(OH)4]2.2H2O (dmen = N,N-dimethyl-1,2-diaminoethane) (3), [Ni(HEen)2][B5O6(OH)4]2 (HEen = N-(2-hydroxyethyl)-1,2-diaminoethane) (4), [Ni(AEN)][B5O6(OH)4].H2O (AEN = 1-(3-azapropyl) -2,4-dimethyl-1,5,8-triazaocta-2,4-dienato(1-)) (5), trans-[Ni(dach)2(H2O)2][Ni(dach)2] [B7O9(OH)5]2.4H2O (dach = 1,2-diaminocyclohexane) (6), and the neutral species trans-[Ni(en)(H2O)2{B6O7(OH)6}].H2O (7) (en = 1,2-diaminoethane), and [Ni(dmen)(H2O){B6O7(OH)6}].5H2O (8). Compounds 1–8 were characterized by single-crystal XRD studies and by IR spectroscopy and 2, 4–7 were also characterized by thermal (TGA/DSC) methods and powder XDR studies. The solid-state structures of all compounds show extensive stabilizing H-bond interactions, important for their formation, and also display a range of gross structural features: 1 has an insular tetraborate(2-) anion, 2–5 have insular pentaborate(1-) anions, 6 has an insular heptaborate(2-) anion (‘O+’ isomer), whilst 7 and 8 have hexaborate(2-) anions directly coordinated to their Ni(II) centers, as bidentate or tridentate ligands, respectively. The Ni(II) centers are either octahedral (1–4, 7, 8) or square-planar (5), and compound 6 has both octahedral and square-planar metal geometries present within the structure as a double salt. Magnetic susceptibility measurements were undertaken on all compounds.
      Citation: Inorganics
      PubDate: 2021-08-31
      DOI: 10.3390/inorganics9090068
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 69: Copper(II) Prevents the
           Saccarine-Dialkylcyanamide Coupling by Forming Mononuclear
           (Saccharinate)(Dialkylcyanamide)copper(II) Complexes

    • Authors: Yulia N. Toikka, Dar’ya V. Spiridonova, Alexander S. Novikov, Nadezhda A. Bokach
      First page: 69
      Abstract: The reaction in the system CuII/sacNa(H)/NCNR2 (sacNa(H) = sodium saccharinate (saccharin); R = Me, Et) results in the formation of the complexes [Cu(sac)2(NCNR2)(H2O)2] (R = Me 1, Et 2) instead of the expected products derived from the saccharin–cyanamide coupling. Complexes 1, 2, and hydrate 1·2H2O were characterized by IR, AAS (Cu%), TGA, and also by single-crystal X-ray diffraction for 1 and 1·2H2O. An integrated computational study of model structure 1 in the gas phase demonstrates that the Cu–Ncyanamide and Cu–Nsac coordination bonds exhibited a single bond character, polarized toward the N atom and almost purely electrostatic, with the calculated vertical total energies for the Cu–Ncyanamide and Cu–Nsac of 43.6 and 156.4 kcal/mol, respectively. These data confirmed that the copper(II) completely blocks the nucleophilic centers of ligands via coordination, thus preventing the saccharin–cyanamide coupling.
      Citation: Inorganics
      PubDate: 2021-09-08
      DOI: 10.3390/inorganics9090069
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 70: Copper Dithiocarbamates: Coordination
           Chemistry and Applications in Materials Science, Biosciences and Beyond

    • Authors: Graeme Hogarth, Damian C. Onwudiwe
      First page: 70
      Abstract: Copper dithiocarbamate complexes have been known for ca. 120 years and find relevance in biology and medicine, especially as anticancer agents and applications in materials science as a single-source precursor (SSPs) to nanoscale copper sulfides. Dithiocarbamates support Cu(I), Cu(II) and Cu(III) and show a rich and diverse coordination chemistry. Homoleptic [Cu(S2CNR2)2] are most common, being known for hundreds of substituents. All contain a Cu(II) centre, being either monomeric (distorted square planar) or dimeric (distorted trigonal bipyramidal) in the solid state, the latter being held together by intermolecular C···S interactions. Their d9 electronic configuration renders them paramagnetic and thus readily detected by electron paramagnetic resonance (EPR) spectroscopy. Reaction with a range of oxidants affords d8 Cu(III) complexes, [Cu(S2CNR2)2][X], in which copper remains in a square-planar geometry, but Cu–S bonds shorten by ca. 0.1 Å. These show a wide range of different structural motifs in the solid-state, varying with changes in anion and dithiocarbamate substituents. Cu(I) complexes, [Cu(S2CNR2)2]−, are (briefly) accessible in an electrochemical cell, and the only stable example is recently reported [Cu(S2CNH2)2][NH4]·H2O. Others readily lose a dithiocarbamate and the d10 centres can either be trapped with other coordinating ligands, especially phosphines, or form clusters with tetrahedral [Cu(μ3-S2CNR2)]4 being most common. Over the past decade, a wide range of Cu(I) dithiocarbamate clusters have been prepared and structurally characterised with nuclearities of 3–28, especially exciting being those with interstitial hydride and/or acetylide co-ligands. A range of mixed-valence Cu(I)–Cu(II) and Cu(II)–Cu(III) complexes are known, many of which show novel physical properties, and one Cu(I)–Cu(II)–Cu(III) species has been reported. Copper dithiocarbamates have been widely used as SSPs to nanoscale copper sulfides, allowing control over the phase, particle size and morphology of nanomaterials, and thus giving access to materials with tuneable physical properties. The identification of copper in a range of neurological diseases and the use of disulfiram as a drug for over 50 years makes understanding of the biological formation and action of [Cu(S2CNEt2)2] especially important. Furthermore, the finding that it and related Cu(II) dithiocarbamates are active anticancer agents has pushed them to the fore in studies of metal-based biomedicines.
      Citation: Inorganics
      PubDate: 2021-09-10
      DOI: 10.3390/inorganics9090070
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 71: The Coordination Chemistry of
           Imidomethanedithiolate Di-anions: A Structural Comparison with Their
           Dithiocarbamate Analogs

    • Authors: Peter J. Heard, Yee Seng Tan, Chien Ing Yeo, Edward R. T. Tiekink
      First page: 71
      Abstract: A review of the coordination chemistry along with the structural features of heavy element complexes of dithiocarbimate di-anions in the form of [(R)C=NCS2]2− for R = CN, alkyl, and aryl are described. This class of compound is far less studied compared with the well-explored dithiocarbamate mono-anions formulated as [R(R’)NCS2]− for R/R’ = H, alkyl, and aryl. The coordination chemistry of dithiocarbimate di-anions is dominated by a S,S-chelating mode; rare examples of alternative modes of coordination are evident. When comparisons are available, the structural motifs adopted by metal dithiocarbimate complexes match those found for their dithiocarbamate analogs, with only small, non-systematic variations in the M–S bond lengths.
      Citation: Inorganics
      PubDate: 2021-09-14
      DOI: 10.3390/inorganics9090071
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 72: Synthesis and Characterization of Super
           Bulky β-Diketiminato Group 1 Metal Complexes

    • Authors: Dafydd D. L. Jones, Samuel Watts, Cameron Jones
      First page: 72
      Abstract: Sterically bulky β-diketiminate (or Nacnac) ligand systems have recently shown the ability to kinetically stabilize highly reactive low-oxidation state main group complexes. Metal halide precursors to such systems can be formed via salt metathesis reactions involving alkali metal complexes of these large ligand frameworks. Herein, we report the synthesis and characterization of lithium and potassium complexes of the super bulky anionic β-diketiminate ligands, known [TCHPNacnac]− and new [TCHP/DipNacnac]− (ArNacnac = [(ArNCMe)2CH]−) (Ar = 2,4,6-tricyclohexylphenyl (TCHP) or 2,6-diisopropylphenyl (Dip)). The reaction of the proteo-ligands, ArNacnacH, with nBuLi give the lithium etherate compounds, [(TCHPNacnac)Li(OEt2)] and [(TCHP/DipNacnac)Li(OEt2)], which were isolated and characterized by multinuclear NMR spectroscopy and X-ray crystallography. The unsolvated potassium salts, [{K(TCHPNacnac)}2] and [{K(TCHP/DipNacnac)}∞], were also synthesized and characterized in solution by NMR spectroscopy. In the solid state, these highly reactive potassium complexes exhibit differing alkali metal coordination modes, depending on the ligand involved. These group 1 complexes have potential as reagents for the transfer of the bulky ligand fragments to metal halides, and for the subsequent stabilization of low-oxidation state metal complexes.
      Citation: Inorganics
      PubDate: 2021-09-16
      DOI: 10.3390/inorganics9090072
      Issue No: Vol. 9, No. 9 (2021)
  • Inorganics, Vol. 9, Pages 59: Synthesis and Antiparasitic Activity of New
           Conjugates—Organic Drugs Tethered to Trithiolato-Bridged Dinuclear
           Ruthenium(II)–Arene Complexes

    • Authors: Oksana Desiatkina, Serena K. Johns, Nicoleta Anghel, Ghalia Boubaker, Andrew Hemphill, Julien Furrer, Emilia Păunescu
      First page: 59
      Abstract: Tethering known drugs to a metalorganic moiety is an efficient approach for modulating the anticancer, antibacterial, and antiparasitic activity of organometallic complexes. This study focused on the synthesis and evaluation of new dinuclear ruthenium(II)–arene compounds linked to several antimicrobial compounds such as dapsone, sulfamethoxazole, sulfadiazine, sulfadoxine, triclosan, metronidazole, ciprofloxacin, as well as menadione (a 1,4-naphtoquinone derivative). In a primary screen, 30 compounds (17 hybrid molecules, diruthenium intermediates, and antimicrobials) were assessed for in vitro activity against transgenic T. gondii tachyzoites constitutively expressing β-galactosidase (T. gondii β-gal) at 0.1 and 1 µM. In parallel, the cytotoxicity in noninfected host cells (human foreskin fibroblasts, HFF) was determined by an alamarBlue assay. When assessed at 1 µM, five compounds strongly impaired parasite proliferation by >90%, and HFF viability was retained at 50% or more, and they were further subjected to T. gondii β-gal dose-response studies. Two compounds, notably 11 and 13, amide and ester conjugates with sulfadoxine and metronidazole, exhibited low IC50 (half-maximal inhibitory concentration) values 0.063 and 0.152 µM, and low or intermediate impairment of HFF viability at 2.5 µM (83 and 64%). The nature of the anchored drug as well as that of the linking unit impacted the biological activity.
      Citation: Inorganics
      PubDate: 2021-07-21
      DOI: 10.3390/inorganics9080059
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 60: Dithiocarbamate Complexes of Platinum Group
           Metals: Structural Aspects and Applications

    • Authors: Yee Seng Tan, Chien Ing Yeo, Edward R. T. Tiekink, Peter J. Heard
      First page: 60
      Abstract: The incorporation of dithiocarbamate ligands in the preparation of metal complexes is largely prompted by the versatility of this molecule. Fascinating coordination chemistry can be obtained from the study of such metal complexes ranging from their preparation, the solid-state properties, solution behavior as well as their applications as bioactive materials and luminescent compounds, to name a few. In this overview, the dithiocarbamate complexes of platinum-group elements form the focus of the discussion. The structural aspects of these complexes will be discussed based upon the intriguing findings obtained from their solid- (crystallographic) and solution-state (NMR) studies. At the end of this review, the applications of platinum-group metal complexes will be discussed.
      Citation: Inorganics
      PubDate: 2021-07-22
      DOI: 10.3390/inorganics9080060
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 61: Testing the Efficacy of the Synthesis of
           Iron Antimony Sulfide Powders from Single Source Precursors

    • Authors: Fadiyah Makin, Dalal Alzahrani, Firoz Alam, Floriana Tuna, David J. Lewis
      First page: 61
      Abstract: The antimony-iron sulfide system in general does not produce alloys below 540 °C from traditional solid-state methods. However, single source precursors have been known to produce unexpected products that arise from kinetically trapped polymorphs. In this paper, we test the efficacy of this approach toward the Fe-Sb-S system. Antimony and iron diethyldithiocarbamate complexes of the form Sb[S2CN(Et2)]3 (1) and Fe[S2CN(Et2)]3 (2) were synthesised, characterised, and used as single-source precursors for the preparation of Sb2S3, FexSy, and mixed iron antimony sulfide Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1) powders using the solvent-less thermolysis method at different temperatures ranging from 300 to 475 °C. The effect of different mole fractions of the iron precursor was evaluated on morphology, shape, and optical and magnetic properties of Sb2(1−x)Fe2xS3 (0 ≥ x ≥ 1). The obtained powders were characterized by X-ray diffraction (XRD), Raman spectroscopy scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, magnetometer measurement, and UV/vis/NIR spectroscopy. The results demonstrated that the crystalline structure, morphology, and elemental composition of the samples changed with the mole fraction of the precursor. There was significant phase separation between Sb and Fe sulfides noted from EDX spectroscopic mapping, yet an optoelectronic study monitoring the direct band gap energy of antimony sulfide shows that the band gap energy increases as a function of Fe content, which suggests limited alloying is possible from the single source route.
      Citation: Inorganics
      PubDate: 2021-08-02
      DOI: 10.3390/inorganics9080061
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 62: Barium Titanium Oxynitride from Ammonia-Free
           Nitridation of Reduced BaTiO3

    • Authors: Hua Guo, Aleksander Jaworski, Zheng Chen, Can Lu, Adam Slabon, Ulrich Häussermann
      First page: 62
      Abstract: We investigated the nitridation of reduced BaTiO3, BaTiO2.60H0.08, corresponding to an oxyhydride with a large concentration of O defects (>10%). The material is readily nitrided under flowing N2 gas at temperatures between 400 and 450 °C to yield oxynitrides BaTiO2.6Nx (x = 0.2−0.22) with a slightly tetragonally distorted perovskite structure, a ≈ 4.01 and c ≈ 4.02 Å, and Ti partially remaining in the oxidation state III. The tetragonal structure was confirmed from Raman spectroscopy. 14N MAS NMR spectroscopy shows a single resonance at 270 ppm, which is typical for perovskite transition metal oxynitrides. However, largely different signal intensity for materials with very similar N content suggests N/O/vacancy ordering when prolonging nitridation times to hours. Diffuse reflectance UV-VIS spectroscopy shows a reduction of the intrinsic band gap to 2.4–2.45 eV compared to BaTiO3 (~3.2 eV). Mott-Schottky measurements confirm n-type conductivity and reveal a slight negative shift of the conduction band edge from –0.59 V (BaTiO3) to ~–0.65 eV.
      Citation: Inorganics
      PubDate: 2021-08-05
      DOI: 10.3390/inorganics9080062
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 63: Effect of Reduced Atmosphere Sintering on
           Blocking Grain Boundaries in Rare-Earth Doped Ceria

    • Authors: Soumitra Sulekar, Mehrad Mehr, Ji Hyun Kim, Juan Claudio Nino
      First page: 63
      Abstract: Rare-earth doped ceria materials are amongst the top choices for use in electrolytes and composite electrodes in intermediate temperature solid oxide fuel cells. Trivalent acceptor dopants such as gadolinium, which mediate the ionic conductivity in ceria by creating oxygen vacancies, have a tendency to segregate at grain boundaries and triple points. This leads to formation of ionically resistive blocking grain boundaries and necessitates high operating temperatures to overcome this barrier. In an effort to improve the grain boundary conductivity, we studied the effect of a modified sintering cycle, where 10 mol% gadolinia doped ceria was sintered under a reducing atmosphere and subsequently reoxidized. A detailed analysis of the complex impedance, conductivity, and activation energy values was performed. The analysis shows that for samples processed thus, the ionic conductivity improves when compared with conventionally processed samples sintered in air. Equivalent circuit fitting shows that this improvement in conductivity is mainly due to a drop in the grain boundary resistance. Based on comparison of activation energy values for the conventionally processed vs. reduced-reoxidized samples, this drop can be attributed to a diminished blocking effect of defect-associates at the grain boundaries.
      Citation: Inorganics
      PubDate: 2021-08-09
      DOI: 10.3390/inorganics9080063
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 64: Switching the Local Symmetry from D5h to D4h
           for Single-Molecule Magnets by Non-Coordinating Solvents

    • Authors: Xia-Li Ding, Qian-Cheng Luo, Yuan-Qi Zhai, Qian Zhang, Lei Tian, Xinliang Zhang, Chao Ke, Xu-Feng Zhang, Yi Lv, Yan-Zhen Zheng
      First page: 64
      Abstract: A solvent effect towards the performance of two single-molecule magnets (SMMs) was observed. The tetrahydrofuran and toluene solvents can switch the equatorial coordinated 4-Phenylpyridine (4-PhPy) molecules from five to four, respectively, in [Dy(OtBu)2(4-PhPy)5]BPh41 and Na{[Dy(OtBu)2(4-PhPy)4][BPh4]2}∙2thf∙hex 2. This alternation significantly changes the local coordination symmetry of the Dy(III) center from D5h to D4h for 1 and 2, seperately. Magnetic studies show that the magnetic anisotropy energy barrier of 2 is higher than that of 1, while the relation of blocking temperature is just on the contrary due to the symmetry effect. The calculations of the electrostatic potential successfully explained the driving force of solvents for the molecular structure change, confirming the feasibility of adjusting the performance of SMMs via diverse solvents.
      Citation: Inorganics
      PubDate: 2021-08-16
      DOI: 10.3390/inorganics9080064
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 65: A New Perspective on Fluorapatite
           Dissolution in Hydrochloric Acid: Thermodynamic Calculations and
           Experimental Study

    • Authors: Kaia Tõnsuaadu, Juha Kallas, Rein Kuusik, Gizem Hacialioglu-Erlenheim, Andres Trikkel
      First page: 65
      Abstract: Apatite (Ap) dissolution in diluted acids is well described in the literature, but in technological processes which use more concentrated acids, the reaction is fast, and it is complicated to follow the process kinetics. The relationship between pH change and the apatite dissolution rate depending on HCl concentration was studied by thermodynamic calculations and experiments with synthetic fluorapatite (FAp). On the basis of experimental pH measurements, the kinetics of dissolution was analyzed. The solution composition (P, Ca, F) was determined by wet chemical methods and the solid part was characterized by XRD and FTIR. It was shown that the amount of HCl needed for FAp dissolution depends on acid concentration. FAp dissolution rate cannot be deduced from solubility data of P, Ca or F as the secondary reactions of CaF2 and CaHPO4 formation take place simultaneously. It was found that the Ap dissolution rate can be followed by pH change.
      Citation: Inorganics
      PubDate: 2021-08-16
      DOI: 10.3390/inorganics9080065
      Issue No: Vol. 9, No. 8 (2021)
  • Inorganics, Vol. 9, Pages 50: Chiral or Luminescent Lanthanide
           Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

    • Authors: Bertrand Lefeuvre, Jessica Flores Gonzalez, Carlo Andrea Mattei, Vincent Dorcet, Olivier Cador, Fabrice Pointillart
      First page: 50
      Abstract: The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam− = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6(L)]·2(C7H16) ((1)·2(C7H16)) and [Dy2((+)facam)6(L)]·2(C6H14) ((2)·2(C6H14)). The X-ray structures reveal that the L triad bridges two terminal Yb(hfac)3 or Dy(facam)3 units. (1)·2(C7H16) behaved as a near infrared YbIII centered emitter and a field-induced Single-Molecule Magnet (SMM) while (2)·2(C6H14) displayed SMM behavior in both zero- and in-dc field. The magnetization mainly relaxes through a Raman process for both complexes under an optimal applied magnetic field.
      Citation: Inorganics
      PubDate: 2021-06-23
      DOI: 10.3390/inorganics9070050
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 51: A Dy(III) Fluorescent Single-Molecule Magnet
           Based on a Rhodamine 6G Ligand

    • Authors: Lin Miao, Mei-Jiao Liu, Man-Man Ding, Yi-Quan Zhang, Hui-Zhong Kou
      First page: 51
      Abstract: The complexes of lanthanide metals, especially dysprosium, can generally exhibit excellent magnetic properties. By means of modifying ligands, dual functions or even multi-functions can be achieved. Here, we synthesized an eight-coordinate Dy(III) complex 1, [Dy(HL-o)2(MeOH)2](ClO4)3·4.5MeOH, which is single-molecule magnet (SMM), and the introduction of the rhodamine 6G chromophore in the ring-opened ligand HL-o realizes ligand-centered fluorescence in addition to SMM. Magnetic measurements and ab initio calculations indicate that the magnetic relaxation for complex 1 should be due to the Raman relaxation process. Studies on magneto-structural correlationship of the rhodamine salicylaldehyde hydrazone Dy(III) complexes show that the calculated energy of the first Kramers Doublet (EKD1) is basically related to the Ophenoxy-Dy-Ophenoxy bond angle, i.e., the larger Ophenoxy-Dy-Ophenoxy bond angle corresponds to a larger EKD1.
      Citation: Inorganics
      PubDate: 2021-06-29
      DOI: 10.3390/inorganics9070051
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 52: Mono- and Dinuclear Aluminium Complexes
           Derived from Biguanide and Carbothiamide Ligands

    • Authors: Maximilian Dehmel, Helmar Görls, Robert Kretschmer
      First page: 52
      Abstract: Dianionic N,N-chelating ligands play a crucial role in coordination chemistry, but reports on related complexes remain limited to certain types of ligands. In here, the reactions of two diprotic ligands, i.e., a biguanide and a carbothiamide, with trimethylaluminium, are reported, which give rise to mono- and dinuclear aluminium(III) complexes. In addition, single deprotonation of the diprotic biguanide using potassium bis(trimethylsilyl)amide gives rise to a one-dimensional coordination polymer. All complexes have been fully characterized, and their solid-state structures were determined by single crystal X-ray diffraction analysis.
      Citation: Inorganics
      PubDate: 2021-07-07
      DOI: 10.3390/inorganics9070052
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 53: Stereochemical Geometries and
           Photoluminescence in Pseudo-Halido-Zinc(II) Complexes. Structural
           Comparison between the Corresponding Cadmium(II) Analogs

    • Authors: Franz A. Mautner, Roland C. Fischer, Ana Torvisco, Nahed M. H. Salem, Amber R. Dugas, Shelby F. Aaron, Sushant P. Sahu, Febee R. Louka, Salah S. Massoud
      First page: 53
      Abstract: Six pseudohalide zinc(II) containing a variety of N-donor auxiliary amines were structurally characterized. These include two mononuclear trigonal bipyramidal [Zn(NTB)(N3)]ClO4·½H2O (3) and [Zn(TPA)(NCS)]ClO4 (4), two distorted octahedral [Zn(1,8-damnph)2(dca)2] (5) and [Zn(8-amq)2(dca)2] (6a) as well as two 1D polymeric chains catena-[Zn(isq)2(μ1,5-dca)2] (7) and catena-[Zn(N,N-Me2en)2(μ1,5-dca)]dca (8), where NTB = tris(2-benzimidazolylmethyl)amine, TPA = tris(2-pyridylmethyl)amine, 1,8-damnph = 1,8-diaminonaphthalene, 8-amq = 8-amino-quinoline, isq = isoquinoline (isq) and N,N-Me2en = N,N-dimethylethylenediamine. In general, with the exception of 6 and 8, the complexes exhibited luminescence emission in MeOH associated with red shift of the emission maxima, and the strongest visible fluorescence peak was detected at 421 nm (λex = 330 nm) in the case of Complex 5.
      Citation: Inorganics
      PubDate: 2021-07-09
      DOI: 10.3390/inorganics9070053
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 54: Isomeric 4,2′:6′,4″- and
           3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl
           Substituents: Effects on the Assembly of Coordination Polymers with
           [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)

    • Authors: Giacomo Manfroni, Simona S. Capomolla, Alessandro Prescimone, Edwin C. Constable, Catherine E. Housecroft
      First page: 54
      Abstract: The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n·2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n·2nC6H5Me, [Cu2(hfacac)4(3)2]n·nC6H4Cl2, [Cu2(hfacac)4(3)2]n·nC6H5Cl, and [Cu(hfacac)2(4)]n·nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2]·H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n·2nC6H4Cl2 and [Cu(hfacac)2(2)]n·2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n·nC6H4Cl2 and [Cu(hfacac)2(4)]n·nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n·nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n·nC6H4Cl2 and [Cu(hfacac)2(4)]n·nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4.
      Citation: Inorganics
      PubDate: 2021-07-10
      DOI: 10.3390/inorganics9070054
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 55: Arene-Osmium(II) Complexes in Homogeneous

    • Authors: Pascale Crochet, Victorio Cadierno
      First page: 55
      Abstract: Although the application of arene-osmium(II) complexes in homogeneous catalysis has been much less studied than that of their ruthenium analogues, different works have shown that, in some instances, a comparable or even superior effectiveness can be achieved with this particular class of compounds. This review article focuses on the catalytic applications of arene-osmium(II) complexes. Among others, transfer hydrogenation, hydrogenation, oxidation, and nitrile hydration reactions, as well as different C-C bond forming processes, are comprehensively discussed.
      Citation: Inorganics
      PubDate: 2021-07-12
      DOI: 10.3390/inorganics9070055
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 56: Application of Metal Halide Perovskites as
           Photocatalysts in Organic Reactions

    • Authors: Marco Corti, Sara Bonomi, Rossella Chiara, Lidia Romani, Paolo Quadrelli, Lorenzo Malavasi
      First page: 56
      Abstract: This review summarizes the current status of the application of metal halide perovskites (MHPs) as photocatalysts in organic syntheses/transformations. It is shown that the optimal and unique electronic properties of MHPs can be advantageously used in several reaction types providing pros with respect to traditional photocatalysts. While still being at infancy, such field of application of MHPs as effective photocatalysts will for sure become a central research topic in the forthcoming years, thanks also to their rich structural and chemical tunability, which may provide tailored materials for most of the envisaged organic reactions.
      Citation: Inorganics
      PubDate: 2021-07-13
      DOI: 10.3390/inorganics9070056
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 57: Ferrocenylmethylphosphanes and the Alpha
           Process for Methoxycarbonylation: The Original Story

    • Authors: Kevin M. Fortune, Christa Castel, Craig M. Robertson, Peter N. Horton, Mark E. Light, Simon J. Coles, Mark Waugh, William Clegg, Ross W. Harrington, Ian R. Butler
      First page: 57
      Abstract: The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours.
      Citation: Inorganics
      PubDate: 2021-07-17
      DOI: 10.3390/inorganics9070057
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 58: Molecular Bottom-Up Approaches for the
           Synthesis of Inorganic and Hybrid Nanostructures

    • Authors: Alberto Escudero, Carolina Carrillo-Carrión, Elena Romero-Ben, Ana Franco, Christian Rosales-Barrios, Mª Carmen Castillejos, Noureddine Khiar
      First page: 58
      Abstract: Chemical routes for the synthesis of nanostructures are fundamental in nanoscience. Among the different strategies for the production of nanostructures, this article reviews the fundamentals of the bottom-up approaches, focusing on wet chemistry synthesis. It offers a general view on the synthesis of different inorganic and hybrid organic–inorganic nanostructures such as ceramics, metal, and semiconductor nanoparticles, mesoporous structures, and metal–organic frameworks. This review article is especially written for a wide audience demanding a text focused on the basic concepts and ideas of the synthesis of inorganic and hybrid nanostructures. It is styled for both early researchers who are starting to work on this topic and also non-specialist readers with a basic background on chemistry. Updated references and texts that provide a deeper discussion and describing the different synthesis strategies in detail are given, as well as a section on the current perspectives and possible future evolution.
      Citation: Inorganics
      PubDate: 2021-07-17
      DOI: 10.3390/inorganics9070058
      Issue No: Vol. 9, No. 7 (2021)
  • Inorganics, Vol. 9, Pages 40: Solvothermal Synthesis Routes to Substituted
           Cerium Dioxide Materials

    • Authors: James W. Annis, Janet M. Fisher, David Thompsett, Richard I. Walton
      First page: 40
      Abstract: We review the solution-based synthesis routes to cerium oxide materials where one or more elements are included in place of a proportion of the cerium, i.e., substitution of cerium is performed. The focus is on the solvothermal method, where reagents are heated above the boiling point of the solvent to induce crystallisation directly from the solution. This yields unusual compositions with crystal morphology often on the nanoscale. Chemical elements from all parts of the periodic table are considered, from transition metals to main group elements and the rare earths, including isovalent and aliovalent cations, and surveyed using the literature published in the past ten years. We illustrate the versatility of this synthesis method to allow the formation of functional materials with applications in contemporary applications such as heterogeneous catalysis, electrodes for solid oxide fuel cells, photocatalysis, luminescence and biomedicine. We pick out emerging trends towards control of crystal habit by use of non-aqueous solvents and solution additives and identify challenges still remaining, including in detailed structural characterisation, the understanding of crystallisation mechanisms and the scale-up of synthesis.
      Citation: Inorganics
      PubDate: 2021-05-21
      DOI: 10.3390/inorganics9060040
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 41: Effects of Glymes on the Distribution of
           Mg(B10H10) and Mg(B12H12) from the Thermolysis of Mg(BH4)2

    • Authors: Ba L. Tran, Tamara N. Allen, Mark E. Bowden, Tom Autrey, Craig M. Jensen
      First page: 41
      Abstract: We examined the effects of concentrations and identities of various glymes, from monoglyme up to tetraglyme, on H2 release from the thermolysis of Mg(BH4)2 at 160–200 °C for 8 h. 11B NMR analysis shows major products of Mg(B10H10) and Mg(B12H12); however, their relative ratio is highly dependent both on the identity and concentration of the glyme to Mg(BH4)2. Selective formation of Mg(B10H10) was observed with an equivalent of monoglyme and 0.25 equivalent of tetraglyme. However, thermolysis of Mg(BH4)2 in the presence of stoichiometric or greater equivalent of glymes can lead to unselective formation of Mg(B10H10) and Mg(B12H12) products or inhibition of H2 release.
      Citation: Inorganics
      PubDate: 2021-05-23
      DOI: 10.3390/inorganics9060041
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 42: Acute Toxicity Evaluation of Non-Innocent
           Oxidovanadium(V) Schiff Base Complex

    • Authors: Lidiane M. A. Lima, Heide Murakami, D. Jackson Gaebler, Wagner E. Silva, Mônica F. Belian, Eduardo C. Lira, Debbie C. Crans
      First page: 42
      Abstract: The vanadium(V) complexes have been investigated as potential anticancer agents which makes it essential to evaluate their toxicity for safe use in the clinic. The large-scale synthesis and the acute oral toxicity in mice of the oxidovanadium(V) Schiff base catecholate complex, abbreviated as [VO(HSHED)dtb] containing a redox-active ligand with tridentate Schiff base (HSHED = N-(salicylideneaminato)-N’-(2-hydroxyethyl)-1,2-ethylenediamine) and dtb = 3,5-di-(t-butyl)catechol ligands were carried out. The body weight, food consumption, water intake as well biomarkers of liver and kidney toxicity of the [VO(HSHED)dtb] were compared to the precursors, sodium orthovanadate, and free ligand. The 10-fold scale-up synthesis of the oxidovanadium(V) complex resulting in the preparation of material in improved yield leading to 2–3 g (79%) material suitable for investigating the toxicity of vanadium complex. No evidence of toxicity was observed in animals when acutely exposed to a single dose of 300 mg/kg for 14 days. The toxicological results obtained with biochemical and hematological analyses did not show significant changes in kidney and liver parameters when compared with reference values. The low oral acute toxicity of the [VO(HSHED)dtb] is attributed to redox chemistry taking place under biological conditions combined with the hydrolytic stability of the oxidovanadium(V) complex. These results document the design of oxidovanadium(V) complexes that have low toxicity but still are antioxidant and anticancer agents.
      Citation: Inorganics
      PubDate: 2021-05-24
      DOI: 10.3390/inorganics9060042
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 43: New Trends in Nanoclay-Modified Sensors

    • Authors: Esperanza Pavón, Rosa Martín-Rodríguez, Ana C. Perdigón, María D. Alba
      First page: 43
      Abstract: Nanoclays are widespread materials characterized by a layered structure in the nano-scale range. They have multiple applications in diverse scientific and industrial areas, mainly due to their swelling capacity, cation exchange capacity, and plasticity. Due to the cation exchange capacity, nanoclays can serve as host matrices for the stabilization of several molecules and, thus, they can be used as sensors by incorporating electroactive ions, biomolecules as enzymes, or fluorescence probes. In this review, the most recent applications as bioanalyte sensors are addressed, focusing on two main detection systems: electrochemical and optical methods. Particularly, the application of electrochemical sensors with clay-modified electrodes (CLME) for pesticide detection is described. Moreover, recent advances of both electrochemical and optical sensors based on nanoclays for diverse bioanalytes’ detection such as glucose, H2O2, organic acids, proteins, or bacteria are also discussed. As it can be seen from this review, nanoclays can become a key factor in sensors’ development, creating an emerging technology for the detection of bioanalytes, with application in both environmental and biomedical fields.
      Citation: Inorganics
      PubDate: 2021-06-02
      DOI: 10.3390/inorganics9060043
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 44:
           Tris-{Hydridotris(1-pyrazolyl)borato}lanthanide Complexes: Synthesis,
           Spectroscopy, Crystal Structure and Bonding Properties

    • Authors: Christos Apostolidis, Attila Kovács, Alfred Morgenstern, Jean Rebizant, Olaf Walter
      First page: 44
      Abstract: Complexes of trivalent lanthanides (Ln) with the hydridotris(1-pyrazolyl)borato (Tp) ligand Ln[η3-HB(N2C3H3)3]3 (LnTp3) were subjected to a joint experimental–theoretical analysis. X-ray diffraction experiments have been performed on CeTp3, NdTp3, SmTp3, GdTp3, and TbTp3 in the nine-fold coordination and on DyTp3, HoTp3, ErTp3, TmTp3, YbTp3, and LuTp3 in the eight-fold coordination form. Density functional theory (DFT) calculations were carried out for all 15 LnTp3 complexes. They extended the X-ray diffraction data available on the LnTp3 compounds and facilitated a straightforward interpretation of trends in the structural parameters. As a result of the joint analysis, significant steric strain in the equatorial coordination sites of the nine-coordinate structures was recognized. Trends in the bonding properties were elucidated by energy decomposition and quantum theory of atoms in molecules (QTAIM) analysis of the electron density distribution. These results revealed the major electrostatic character of the Ln…Tp bonding and fine variation of charge transfer effects across the Ln row.
      Citation: Inorganics
      PubDate: 2021-06-03
      DOI: 10.3390/inorganics9060044
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 45: Volumetrics of Hydrogen Storage by Physical

    • Authors: Sai Smruti Samantaray, Seth T. Putnam, Nicholas P. Stadie
      First page: 45
      Abstract: Physical adsorption remains a promising method for achieving fast, reversible hydrogen storage at both ambient and cryogenic conditions. Research in this area has recently shifted to focus primarily on the volumetric (H2 stored/delivered per volume) gains achieved within an adsorptive storage system over that of pure H2 compression; however, the methodology for estimating a volumetric stored or delivered amount requires several assumptions related to the ultimate packing of the adsorbent material into an actual storage system volume. In this work, we critically review the different assumptions commonly employed, and thereby categorize and compare the volumetric storage and delivery across numerous different porous materials including benchmark metal-organic frameworks, porous carbons, and zeolites. In several cases, there is a significant gain in both storage and delivery by the addition of an adsorbent to the high-pressure H2 storage system over that of pure compression, even at room temperature. Lightweight, low-density materials remain the optimal adsorbents at low temperature, while higher density, open metal-containing frameworks are necessary for high-density room temperature storage and delivery.
      Citation: Inorganics
      PubDate: 2021-06-04
      DOI: 10.3390/inorganics9060045
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 46: Strike a Balance: Between Metals and
           Non-Metals, Metalloids as a Source of Anti-Infective Agents

    • Authors: Tiziano Marzo, Diego La Mendola
      First page: 46
      Abstract: Most of the commercially available anti-infective agents are organic molecules. In fact, though, during the pioneering times of modern medicine, at the beginning of the 20th century, several inorganic compounds of transition metals were used for medicinal application, to date, only a small number of inorganic drugs are used in clinical practice. Beyond the transition metals, metalloids—or semimetals—offer a rich chemistry in between that of metallic and non-metallic elements, and accordingly, peculiar features for their exploitation in medicinal chemistry. A few important examples of metalloid-based drugs currently used for the treatment of various diseases do exist. However, the use of this group of elements could be further expanded on the basis of their current applications and the clinical trials they entered. Considering that metalloids offer the opportunity to expand the “chemical-space” for developing novel anti-infective drugs and protocols, in this paper, we briefly recapitulate and discuss the current applications of B-, Si-, As-, Sb- and Te-based anti-infective drugs.
      Citation: Inorganics
      PubDate: 2021-06-04
      DOI: 10.3390/inorganics9060046
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 47: DFT Investigation of the Molecular
           Properties of the Dimethylglyoximato Complexes [M(Hdmg)2] (M = Ni, Pd, Pt)

    • Authors: Maryam Niazi, Axel Klein
      First page: 47
      Abstract: Important applications of the NiII, PdII and PtII complexes [M(Hdmg)2] (H2dmg = dimethylglyoxime) stem from their metal...metal stacked virtually insoluble aggregates. Given the virtual insolubility of the materials, we postulated that the rare reports on dissolved species in solution do not represent monomolecular species but oligomers. We thus studied the structural and spectral properties of the monomolecular entities of these compounds using density functional theory (DFT) and time-dependent DFT computations in dimethyl sulfoxide (DMSO) as a solvent. The molecular geometries, IR and UV-vis spectra, and frontier orbitals properties were computed using LANL2DZ ecp and def2TZVP as basis sets and M06-2X as the functional. The results are compared with the available experimental and other calculated data. The optimised molecular geometries proved the asymmetric character of the two formed O–H…O bonds which connect the two Hdmg‒ ligands in the completely planar molecules. Calculated UV-vis spectra revealed the presence of three absorptions in the range 180 to 350 nm that are red-shifted along the series Ni–Pd–Pt. They were assigned to essentially ligand-centred π−π* transitions in part with metal(d) to ligand(π*) charge transfer (MLCT) contributions. The notorious d‒p transitions dominating the colour and electronics of the compounds in the solid-state and oligomeric stacks are negligible in our monomolecular models strongly supporting the idea that the previously reported spectroscopic observations or biological effects in solutions are not due to monomolecular complexes but rather to oligomeric dissolved species.
      Citation: Inorganics
      PubDate: 2021-06-07
      DOI: 10.3390/inorganics9060047
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 48: Insights into the Antimicrobial Potential of
           Dithiocarbamate Anions and Metal-Based Species

    • Authors: Chien Ing Yeo, Edward R. T. Tiekink, Jactty Chew
      First page: 48
      Abstract: Bacterial infection remains a worldwide problem that requires urgent addressing. Overuse and poor disposal of antibacterial agents abet the emergence of bacterial resistance mechanisms. There is a clear need for new approaches for the development of antibacterial therapeutics. Herein, the antibacterial potential of molecules based on dithiocarbamate anions, of general formula R(R’)NCS2(−), and metal salts of transition metals and main group elements, is summarized. Preclinical studies show a broad range of antibacterial potential, and these investigations are supported by appraisals of possible biological targets and mechanisms of action to guide chemical syntheses. This bibliographic review of the literature points to the exciting potential of dithiocarbamate-based therapeutics in the crucial battle against bacteria. Additionally, included in this overview, for the sake of completeness, is mention of the far fewer studies on the antifungal potential of dithiocarbamates and even less work conducted on antiparasitic behavior.
      Citation: Inorganics
      PubDate: 2021-06-14
      DOI: 10.3390/inorganics9060048
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 49: Binding Properties of a Dinuclear Zinc(II)
           Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of
           Lewis Acid-Base Adducts with Diamines

    • Authors: Gabriella Munzi, Giuseppe Consiglio, Salvatore Failla, Santo Di Bella
      First page: 49
      Abstract: In this paper we report the binding properties, by combined 1H NMR, optical absorption, and fluorescence studies, of a molecular tweezer composed of two Zn(salen)-type Schiff-base units connected by a flexible spacer, towards a series of ditopic diamines having a strong Lewis basicity, with different chain length and rigidity. Except for the 1,2-diaminoethane, in all other cases the formation of stable 1:1 Lewis acid-base adducts with large binding constants is demonstrated. For α,ω-aliphatic diamines, binding constants progressively increase with the increasing length of the alkyl chain, thanks to the flexible nature of the spacer and the parallel decreased conformational strain upon binding. Stable adducts are also found even for short diamines with rigid molecular structures. Given their preorganized structure, these latter species are not subjected to loss of degrees of freedom. The binding characteristics of the tweezer have been exploited for the colorimetric and fluorometric selective and sensitive detection of piperazine.
      Citation: Inorganics
      PubDate: 2021-06-16
      DOI: 10.3390/inorganics9060049
      Issue No: Vol. 9, No. 6 (2021)
  • Inorganics, Vol. 9, Pages 29: Study of Anharmonicity in Zirconium Hydrides
           Using Inelastic Neutron Scattering and Ab-Initio Computer Modeling

    • Authors: Jiayong Zhang, Yongqiang Cheng, Alexander I. Kolesnikov, Jerry Bernholc, Wenchang Lu, Anibal J. Ramirez-Cuesta
      First page: 29
      Abstract: The anharmonic phonon behavior in zirconium hydrides and deuterides, including ϵ-ZrH2, γ-ZrH, and γ-ZrD, has been investigated from aspects of inelastic neutron scattering (INS) and lattice dynamics calculations within the framework of density functional theory (DFT). The harmonic model failed to reproduce the spectral features observed in the experimental data, indicating the existence of anharmonicity in those materials and the necessity of further explanations. Here, we present a detailed study on the anharmonicity in zirconium hydrides/deuterides by exploring the 2D potential energy surface of hydrogen/deuterium atoms and solving the corresponding 2D single-particle Schrödinger equation to obtain the eigenfrequencies, which are then convoluted with the instrument resolution. The convoluted INS spectra qualitatively describe the anharmonic peaks in the experimental INS spectra and demonstrate that the anharmonicity originates from the deviations of hydrogen potentials from quadratic behavior in certain directions; the effects are apparent for the higher-order excited vibrational states, but small for the ground and first excited states.
      Citation: Inorganics
      PubDate: 2021-04-21
      DOI: 10.3390/inorganics9050029
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 30: Synthesis and Characterisation of Molecular
           Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds

    • Authors: Joseph P. A. Ostrowski, Ashley J. Wooles, Stephen T. Liddle
      First page: 30
      Abstract: Separate reactions of [Th{N(CH2CH2NSiMe2But)2(CH2CH2NSi(Me)(But)(μ-CH2)]2 (1) with [Re(η5-C5H5)2(H)] (2) or [Ru(η5-C5H5)(H)(CO)2] (3) produced, by alkane elimination, [Th(TrenDMBS)Re(η5-C5H5)2] (ThRe, TrenDMBS = {N(CH2CH2NSiMe2But)3}3-), and [Th(TrenDMBS)Ru(η5-C5H5)(CO)2] (ThRu), which were isolated in crystalline yields of 71% and 62%, respectively. Complex ThRe is the first example of a molecular Th-Re bond to be structurally characterised, and ThRu is only the second example of a structurally authenticated Th-Ru bond. By comparison to isostructural U-analogues, quantum chemical calculations, which are validated by IR and Raman spectroscopic data, suggest that the Th-Re and Th-Ru bonds reported here are more ionic than the corresponding U-Re and U-Ru bonds.
      Citation: Inorganics
      PubDate: 2021-04-21
      DOI: 10.3390/inorganics9050030
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 31: Assessing the Intrinsic Strengths of
           Ion–Solvent and Solvent–Solvent Interactions for Hydrated Mg2+

    • Authors: Alexis Antoinette Ann Delgado, Daniel Sethio, Elfi Kraka
      First page: 31
      Abstract: Information resulting from a comprehensive investigation into the intrinsic strengths of hydrated divalent magnesium clusters is useful for elucidating the role of aqueous solvents on the Mg2+ ion, which can be related to those in bulk aqueous solution. However, the intrinsic Mg–O and intermolecular hydrogen bond interactions of hydrated magnesium ion clusters have yet to be quantitatively measured. In this work, we investigated a set of 17 hydrated divalent magnesium clusters by means of local vibrational mode force constants calculated at the ωB97X-D/6-311++G(d,p) level of theory, where the nature of the ion–solvent and solvent–solvent interactions were interpreted from topological electron density analysis and natural population analysis. We found the intrinsic strength of inner shell Mg–O interactions for [Mg(H2O)n]2+ (n = 1–6) clusters to relate to the electron density at the bond critical point in Mg–O bonds. From the application of a secondary hydration shell to [Mg(H2O)n]2+ (n = 5–6) clusters, stronger Mg–O interactions were observed to correspond to larger instances of charge transfer between the lp(O) orbitals of the inner hydration shell and the unfilled valence shell of Mg. As the charge transfer between water molecules of the first and second solvent shell increased, so did the strength of their intermolecular hydrogen bonds (HBs). Cumulative local vibrational mode force constants of explicitly solvated Mg2+, having an outer hydration shell, reveal a CN of 5, rather than a CN of 6, to yield slightly more stable configurations in some instances. However, the cumulative local mode stretching force constants of implicitly solvated Mg2+ show the six-coordinated cluster to be the most stable. These results show that such intrinsic bond strength measures for Mg–O and HBs offer an effective way for determining the coordination number of hydrated magnesium ion clusters.
      Citation: Inorganics
      PubDate: 2021-04-22
      DOI: 10.3390/inorganics9050031
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 32: Recent Progress on Supramolecular
           Luminescent Assemblies Based on Aurophilic Interactions in Solution

    • Authors: Guillermo Romo-Islas, Raquel Gavara
      First page: 32
      Abstract: The development of supramolecular systems showing aurophilic interactions in solution is gaining much attention in the last years. This is due to the intriguing photophysical properties of gold(I) complexes, which usually confer to these supramolecular assemblies interesting luminescent properties, as well as the possibility of morphological modulation, through fine tuning of inter- and intramolecular aurophilic interactions, in synergy with the formation of other supramolecular contacts. In this work, an overview of the advances made in this area since 2015 is presented. A large variety of systems showing different spectroscopical and structural topologies has been reported. Moreover, these supramolecular assemblies have proven to be useful in a wide range of applications.
      Citation: Inorganics
      PubDate: 2021-04-22
      DOI: 10.3390/inorganics9050032
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 33: Editorial for Special Issue “Functional
           Coordination Polymers and Metal–Organic Frameworks”

    • Authors: Rossin
      First page: 33
      Abstract: Metal–Organic Frameworks (MOFs) and Coordination Polymers (CPs) are at theforefront of contemporary coordination chemistry research[…]
      Citation: Inorganics
      PubDate: 2021-05-03
      DOI: 10.3390/inorganics9050033
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 34: Synthesis and Structural Characterization of
           Half-Sandwich Arene–Ruthenium(II) Complexes with
           Bis(imidazol-1-yl)methane, Imidazole and Benzimidazole

    • Authors: Vladislava V. Matveevskaya, Dmitry I. Pavlov, Denis G. Samsonenko, Ekaterina A. Ermakova, Lyubov S. Klyushova, Sergey V. Baykov, Vadim P. Boyarskiy, Andrei S. Potapov
      First page: 34
      Abstract: Mono- and binuclear arene–ruthenium(II) complexes with imidazole-containing ligands were prepared by the reaction of the ligands (L1 = bis(imidazole-1-yl)methane; ImH = 1H-Imidazole; BImH = 1H-Benzimidazole) with [(p-cym)Ru(µ-Cl)2]2 dimers. When bis(imidazole-1-yl)methane reacted with [(p-cym)Ru(µ-Cl)2]2 in methanol, a binuclear complex of the type [Ru2(L1)2(p-cym)2Cl2]Cl2 (2) with cyclic structure was synthesized, whereas by using acetonitrile as a solvent under the same reaction conditions, an unexpected C–N bond cleavage was observed, and a complex of formula [Ru(ImH)2(p-cym)Cl]Cl (1) with coordinated imidazole molecules was obtained. Another type of arene–ruthenium complex [Ru(BImH)(p-cym)Cl2] (3) was obtained by the reaction of benzimidazole and [(p-cym)Ru(µ-Cl)2]2. All compounds were characterized by spectral (FT-IR, NMR 1H, 13C) and single-crystal X-ray diffraction methods; their catalytic activity in transfer hydrogenation and the cytotoxicity against MCF-7 and HepG2 cells were evaluated.
      Citation: Inorganics
      PubDate: 2021-05-04
      DOI: 10.3390/inorganics9050034
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 35: A New Complex Borohydride LiAl(BH4)2Cl2

    • Authors: Oleksandr Dolotko, Takeshi Kobayashi, Ihor Z. Hlova, Shalabh Gupta, Vitalij K. Pecharsky
      First page: 35
      Abstract: A new mixed alkali metal–aluminum borohydride LiAl(BH4)2Cl2 has been prepared via mechanochemical synthesis from the 2LiBH4–AlCl3 mixture. Structural characterization, performed using a combination of X-ray powder diffraction and solid-state NMR methods, indicates that the LiAl(BH4)2Cl2 phase adopts a unique 3D framework and crystallizes in an orthorhombic structure with the space group C2221, a = 11.6709(6) Å, b = 8.4718(4) Å, c = 7.5114(3) Å. The material shows excellent dehydrogenation characteristics, where hydrogen evolution starts at Tons = 70 °C, releasing approximately 2 wt.% of nearly pure (99.8 vol.%) hydrogen and a very small amount (~0.2 vol.%) of diborane. When compared to halide-free mixed alkali metal–aluminum borohydrides, the presence of Al‒Cl bonding in the LiAl(BH4)2Cl2 structure likely prevents the formation of Al(BH4)3 upon decomposition, thus suppressing the formation of diborane.
      Citation: Inorganics
      PubDate: 2021-05-04
      DOI: 10.3390/inorganics9050035
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 36: Roles of Ti-Based Catalysts on Magnesium
           Hydride and Its Hydrogen Storage Properties

    • Authors: Chengshang Zhou, Jingxi Zhang, Robert C. Bowman, Zhigang Zak Fang
      First page: 36
      Abstract: Magnesium-based hydrides are considered as promising candidates for solid-state hydrogen storage and thermal energy storage, due to their high hydrogen capacity, reversibility, and elemental abundance of Mg. To improve the sluggish kinetics of MgH2, catalytic doping using Ti-based catalysts is regarded as an effective approach to enhance Mg-based materials. In the past decades, Ti-based additives, as one of the important groups of catalysts, have received intensive endeavors towards the understanding of the fundamental principle of catalysis for the Mg-H2 reaction. In this review, we start with the introduction of fundamental features of magnesium hydride and then summarize the recent advances of Ti-based additive doped MgH2 materials. The roles of Ti-based catalysts in various categories of elemental metals, hydrides, oxides, halides, and intermetallic compounds were overviewed. Particularly, the kinetic mechanisms are discussed in detail. Moreover, the remaining challenges and future perspectives of Mg-based hydrides are discussed.
      Citation: Inorganics
      PubDate: 2021-05-06
      DOI: 10.3390/inorganics9050036
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 37: Scaling up Metal Hydrides for Real-Scale
           Applications: Achievements, Challenges and Outlook

    • Authors: Emil H. Jensen, Martin Dornheim, Sabrina Sartori
      First page: 37
      Abstract: As the world evolves, so does the energy demand. The storage of hydrogen using metal hydrides shows great promise due to the ability to store and deliver energy on demand while achieving higher volumetric density and safer storage conditions compared with traditional storage options such as compressed gas or liquid hydrogen. Research is typically performed on lab-sized samples and tanks and shows great potential for large scale applications. However, the effects of scale-up on the metal hydride’s performance are relatively less investigated. Studies performed so far on both materials, and hydride-based storage tanks show that the scale-up can significantly impact the system’s capacity, kinetics, and sorption properties. The findings presented in this review suggest areas of further investigation in order to implement metal hydrides in real scale applications.
      Citation: Inorganics
      PubDate: 2021-05-07
      DOI: 10.3390/inorganics9050037
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 38: A Quasi-Intramolecular Solid-Phase Redox
           Reaction of Ammonia Ligands and Perchlorate Anion in Diamminesilver(I)

    • Authors: Lara Alexandre Fogaça, Laura Bereczki, Vladimir M. Petruševski, Berta Barta-Holló, Fernanda Paiva Franguelli, Miklós Mohai, Kende Attila Béres, Istvan E Sajó, Imre Miklós Szilágyi, Laszlo Kotai
      First page: 38
      Abstract: The reaction of ammoniacal AgNO3 solution (or aq. solution of [Ag(NH3)2]NO3) with aq. NaClO4 resulted in [Ag(NH3)2]ClO4 (compound 1). Detailed spectroscopic (correlation analysis, IR, Raman, and UV) analyses were performed on [Ag(NH3)2]ClO4. The temperature and enthalpy of phase change for compound 1 were determined to be 225.7 K and 103.04 kJ/mol, respectively. We found the thermal decomposition of [Ag(NH3)2]ClO4 involves a solid-phase quasi-intramolecular redox reaction between the perchlorate anion and ammonia ligand, resulting in lower valence chlorine oxyacid (chlorite, chlorate) components. We did not detect thermal ammonia loss during the formation of AgClO4. However, a redox reaction between the ammonia and perchlorate ion resulted in intermediates containing chlorate/chlorite, which disproportionated (either in the solid phase or in aqueous solutions after the dissolution of these decomposition intermediates in water) into AgCl and silver perchlorate. We propose that the solid phase AgCl-AgClO4 mixture eutectically melts, and the resulting AgClO4 decomposes in this melt into AgCl and O2. Thus, the final product of decomposition is AgCl, N2, and H2O. The intermediate (chlorite, chlorate) phases were identified by IR, XPS, and titrimetric methods.
      Citation: Inorganics
      PubDate: 2021-05-09
      DOI: 10.3390/inorganics9050038
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 39: The Influence of Co-Precipitation Technique
           on the Structure, Morphology and Dual-Modal Proton Relaxivity of GdFeO3

    • Authors: Yamen Albadi, Maria S. Ivanova, Leonid Y. Grunin, Kirill D. Martinson, Maria I. Chebanenko, Svetlana G. Izotova, Vladimir N. Nevedomskiy, Rufat S. Abiev, Vadim I. Popkov
      First page: 39
      Abstract: Nanocrystals of gadolinium orthoferrite (GdFeO3) with morphology close to isometric and superparamagnetic behavior were successfully synthesized using direct, reverse and microreactor co-precipitation of gadolinium and iron(III) hydroxides with their subsequent heat treatment in the air. The obtained samples were investigated by PXRD, FTIR, low-temperature nitrogen adsorption-desorption measurements, HRTEM, SAED, DRS and vibration magnetometry. According to the X-ray diffraction patterns, the GdFeO3 nanocrystals obtained using direct co-precipitation have the smallest average size, while the GdFeO3 nanocrystals obtained using reverse and microreactor co-precipitation have approximately the same average size. It was shown that the characteristic particle size values are much larger than the corresponding values of the average crystallite size, which indicates the aggregation of the obtained GdFeO3 nanocrystals. The GdFeO3 nanocrystals obtained using direct co-precipitation aggregate more than the GdFeO3 nanocrystals obtained using reverse co-precipitation, which, in turn, tend to aggregate more strongly than the GdFeO3 nanocrystals obtained using microreactor co-precipitation. The bandgap of the obtained GdFeO3 nanocrystals decreases with decreasing crystallite size, which is apparently due to their aggregation. The colloidal solutions of the obtained GdFeO3 nanocrystals with different concentrations were investigated by 1H NMR to measure the T1 and T2 relaxation times. Based on the obtained r2/r1 ratios, the GdFeO3 nanocrystals obtained using microreactor, direct and reverse co-precipitation may be classified as T1, T2 and T1–T2 dual-modal MRI contrast agents, respectively.
      Citation: Inorganics
      PubDate: 2021-05-12
      DOI: 10.3390/inorganics9050039
      Issue No: Vol. 9, No. 5 (2021)
  • Inorganics, Vol. 9, Pages 21: Photocatalytic Activity of Multicompound
           TiO2/SiO2 Nanoparticles

    • Authors: Filipp Temerov, Janne Haapanen, Jyrki M. Mäkelä, Jarkko J. Saarinen
      First page: 21
      Abstract: Multicompound TiO2/SiO2 nanoparticles with a diameter of 50–70 nm were generated using a liquid flame spray (LFS) nanoparticle deposition in a single flame. Here, we study the photocatalytic activity of deposited multicompound nanoparticles in gas-phase via oxidation of acetylene into carbon dioxide that gives new insight about the multicompound nanoparticle morphology. A small addition of SiO2 content of 0.5%, 1.0% and 3.0% significantly suppressed the photocatalytic activity by 33%, 44% and 70%, respectively, whereas 5.0% SiO2 addition completely removed the activity. This may be due to a formation of a thin passivating SiO2 layer on top of the of the TiO2 nanostructures during the LFS nanoparticle deposition. Surface wetting results support this hypothesis with a significant increase in water contact angle as the SiO2 content is increased.
      Citation: Inorganics
      PubDate: 2021-03-25
      DOI: 10.3390/inorganics9040021
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 22: Broadening the Scope of Polyoxometalates as
           Artificial Proteases in Surfactant Solutions: Hydrolysis of Ovalbumin by
           Zr(IV)-Substituted Keggin Complex

    • Authors: Nada D. Savić, David E. Salazar Marcano, Thomas Quanten, Tatjana N. Parac-Vogt
      First page: 22
      Abstract: Development of catalysts for the selective hydrolysis of proteins is challenging, yet important for many applications in biotechnology and proteomics. The hydrolysis of hydrophobic proteins is particularly challenging, as due to their poor solubility, the use of surfactants is often required. In this study, the proteolytic potential of catalyst systems based on the Zr(IV)-substituted Keggin polyoxometalate (Et2NH2)10[Zr(PW11O39)2] (Zr-K 1:2) and three different surfactants (ionic SDS (sodium dodecyl sulfate); zwitterionic Zw3-12 (n-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate); and CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate)), which differ in structure and polarity, has been investigated. Hydrolysis of ovalbumin (OVA) was examined in the presence of Zr-K 1:2 and surfactants by sodium dodecyl sulfate poly(acrylamide) gel electrophoresis (SDS-PAGE), which showed the appearance of new polypeptide fragments at lower molecular weight, indicating that selective hydrolysis of OVA took place for all three catalyst systems. The same fragmentation pattern was observed, showing that the selectivity was not affected by surfactants. However, the surfactants influenced the performance of the catalyst. Hence, the interactions of OVA with surfactants and Zr-K 1:2 were investigated using different techniques such as tryptophan fluorescence, Circular Dichroism, and Dynamic Light Scattering. The speciation of the catalyst in surfactant solutions was also followed by 31P Nuclear Magnetic Resonance spectroscopy providing insight into its stability under reaction conditions.
      Citation: Inorganics
      PubDate: 2021-03-26
      DOI: 10.3390/inorganics9040022
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 23: Optimization of the Synthesis and Energy
           Transfer of Ca2MgWO6:Cr3+,Nd3+

    • Authors: Viktor Anselm, Thomas Jüstel
      First page: 23
      Abstract: This work pertains to Cr3+ and Nd3+ co-activated Ca2MgWO6 phosphors synthesized by high temperature solid-state method using oxides and carbonates as raw materials. All luminescent samples according to Ca2MgWO6:Cr3+,Nd3+ include Cr3+ for the absorption of UV and visible radiation (230–800 nm) prior to energy transfer to Nd3+. As a result of the energy transfer between Cr3+ and Nd3+, we observe line emission originating from Nd3+ in the near infrared range additionally to the broad band near infrared emission from Cr3+ assigned to the spin-allowed 4T2 → 4A2 transition. The energy transfer from Cr3+ to Nd3+ is discussed via the variations of the lifetime data of Cr3+ and Nd3+. The strong absorption of Cr3+ in the ultraviolet range and the efficient energy transfer from Cr3+ to Nd3+ indicate that the herein presented material type can serve as a radiation converter for near infrared region light emitting diodes (NIR-LEDs) comprising an UV-A emitting (Al,Ga)N chip.
      Citation: Inorganics
      PubDate: 2021-03-31
      DOI: 10.3390/inorganics9040023
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 24: Synthesis of a Ru(II) Complex with a
           Naphthoquinone-Annelated Imidazole Ligand Exhibiting Proton-Responsive
           Redox and Luminescent Behavior

    • Authors: Takuya Shiga, Minami Tachibana, Hiroki Oshio, Masayuki Nihei
      First page: 24
      Abstract: A mononuclear ruthenium complex, [RuII(L)(bpy)2](PF6), with a naphthoquinone-annelated imidazole ligand HL (2-(pyridin-2-yl)-1H-naphtho[2,3-d]imidazole-4,9-dione) was synthesized and structurally characterized. Electrochemical study reveals that the Ru complex shows four reversible redox waves at +0.98 V, −1.13 V, −1.53 V, and −1.71 V versus SCE in acetonitrile, which are assigned to Ru(II)/Ru(III), L−/L•2−, and two bpy/bpy•− redox couples, respectively. The redox potential of Ru(II)/Ru(III) was positively shifted upon the addition of trifluoromethanesulfonic acid due to protonation of the L− moiety, leading to stabilization of the Ru 4d orbital. In UV-vis absorption measurements for the Ru complex in acetonitrile, a metal-to-ligand charge transfer (MLCT) band was observed at 476 nm, which was shifted to 450 nm by protonation, which might be due to a decrease in the electron delocalization and stabilization of the π orbitals in L−. The blue shift of the MLCT band by protonation was associated with a shift of an emission band from 774 nm to 620 nm, which could be caused by the decreased electronic delocalization in the MLCT excited state. These electrochemical and spectroscopic changes were reversible for the protonation/deprotonation stimuli.
      Citation: Inorganics
      PubDate: 2021-04-03
      DOI: 10.3390/inorganics9040024
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 25: Hydrothermal Synthesis and Structural
           Investigation of a Crystalline Uranyl Borosilicate

    • Authors: Kristen A. Pace, Vladislav V. Klepov, Mark D. Smith, Travis Williams, Gregory Morrison, Jochen A. Lauterbach, Scott T. Misture, Hans-Conrad zur Loye
      First page: 25
      Abstract: The relevance of multidimensional and porous crystalline materials to nuclear waste remediation and storage applications has motivated exploratory research focused on materials discovery of compounds, such as actinide mixed-oxoanion phases, which exhibit rich structural chemistry. The novel phase K1.8Na1.2[(UO2)BSi4O12] has been synthesized using hydrothermal methods, representing the first example of a uranyl borosilicate. The three-dimensional structure crystallizes in the orthorhombic space group Cmce with lattice parameters a = 15.5471(19) Å, b = 14.3403(17) Å, c = 11.7315(15) Å, and V = 2615.5(6) Å3, and is composed of UO6 octahedra linked by [BSi4O12]5− chains to form a [(UO2)BSi4O12]3− framework. The synthesis method, structure, results of Raman, IR, and X-ray absorption spectroscopy, and thermal stability are discussed.
      Citation: Inorganics
      PubDate: 2021-04-06
      DOI: 10.3390/inorganics9040025
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 26: Anticancer Half-Sandwich Rhodium(III)

    • Authors: Klaudia Máliková, Lukáš Masaryk, Pavel Štarha
      First page: 26
      Abstract: Platinum-based anticancer drugs are most likely the most successful group of bioinorganic compounds. Their apparent disadvantages have led to the development of anticancer compounds of other noble metals, resulting in several ruthenium-based drugs which have entered clinical trials on oncological patients. Besides ruthenium, numerous rhodium complexes have been recently reported as highly potent antiproliferative agents against various human cancer cells, making them potential alternatives to Pt- and Ru-based metallodrugs. In this review, half-sandwich Rh(III) complexes are overviewed. Many representatives show higher in vitro potency than and different mechanisms of action (MoA) from the conventional anticancer metallodrugs (cisplatin in most cases) or clinically studied Ru drug candidates. Furthermore, some of the reviewed Rh(III) arenyl complexes are also anticancer in vivo. Pioneer anticancer organorhodium compounds as well as the recent advances in the field are discussed properly, and adequate attention is paid to their anticancer activity, solution behaviour and various processes connected with their MoA. In summary, this work summarizes the types of compounds and the most important biological results obtained in the field of anticancer half-sandwich Rh complexes.
      Citation: Inorganics
      PubDate: 2021-04-08
      DOI: 10.3390/inorganics9040026
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 27: Metal–Organic Frameworks as Versatile
           Platforms for Organometallic Chemistry

    • Authors: Fan Chen, Hannah F. Drake, Liang Feng, Joshua A. Powell, Kun-Yu Wang, Tian-Hao Yan, Hong-Cai Zhou
      First page: 27
      Abstract: Metal–organic frameworks (MOFs) are emerging porous materials with highly tunable structures developed in the 1990s, while organometallic chemistry is of fundamental importance for catalytic transformation in the academic and industrial world for many decades. Through the years, organometallic chemistry has been incorporated into functional MOF construction for diverse applications. Here, we will focus on how organometallic chemistry is applied in MOF design and modifications from linker-centric and metal-cluster-centric perspectives, respectively. Through structural design, MOFs can function as a tailorable platform for traditional organometallic transformations, including reaction of alkenes, cross-coupling reactions, and C–H activations. Besides, an overview will be made on other application categories of organometallic MOFs, such as gas adsorption, magnetism, quantum computing, and therapeutics.
      Citation: Inorganics
      PubDate: 2021-04-09
      DOI: 10.3390/inorganics9040027
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 28: Metal-Rich Metallaboranes: Synthesis,
           Structures and Bonding of Bi- and Trimetallic Open-Faced Cobaltaboranes

    • Authors: Kriti Pathak, Chandan Nandi, Jean-François Halet, Sundargopal Ghosh
      First page: 28
      Abstract: Synthesis, isolation, and structural characterization of unique metal rich diamagnetic cobaltaborane clusters are reported. They were obtained from reactions of monoborane as well as modified borohydride reagents with cobalt sources. For example, the reaction of [Cp*CoCl]2 with [LiBH4·THF] and subsequent photolysis with excess [BH3·THF] (THF = tetrahydrofuran) at room temperature afforded the 11-vertex tricobaltaborane nido-[(Cp*Co)3B8H10] (1, Cp* = η5-C5Me5). The reaction of Li[BH2S3] with the dicobaltaoctaborane(12) [(Cp*Co)2B6H10] yielded the 10-vertex nido-2,4-[(Cp*Co)2B8H12] cluster (2), extending the library of dicobaltadecaborane(14) analogues. Although cluster 1 adopts a classical 11-vertex-nido-geometry with one cobalt center and four boron atoms forming the open pentagonal face, it disobeys the Polyhedral Skeletal Electron Pair Theory (PSEPT). Compound 2 adopts a perfectly symmetrical 10-vertex-nido framework with a plane of symmetry bisecting the basal boron plane resulting in two {CoB3} units bridged at the base by two boron atoms and possesses the expected electron count. Both compounds were characterized in solution by multinuclear NMR and IR spectroscopies and by mass spectrometry. Single-crystal X-ray diffraction analyses confirmed the structures of the compounds. Additionally, density functional theory (DFT) calculations were performed in order to study and interpret the nature of bonding and electronic structures of these complexes.
      Citation: Inorganics
      PubDate: 2021-04-13
      DOI: 10.3390/inorganics9040028
      Issue No: Vol. 9, No. 4 (2021)
  • Inorganics, Vol. 9, Pages 18: CO2 Derivatives of Molecular Tin Compounds.
           Part 2: Carbamato, Formato, Phosphinoformato and Metallocarboxylato

    • Authors: Laurent Plasseraud
      First page: 18
      Abstract: Single-crystal X-ray diffraction structures of organotin compounds bearing hemicarbonate and carbonate ligands were recently reviewed by us—“CO2 Derivatives of Molecular Tin Compounds. Part 1: Hemicarbonato and Carbonato Complexes”, Inorganics 2020, 8, 31—based on crystallographic data available from the Cambridge Structural Database. Interestingly, this first collection revealed that most of the compounds listed were isolated in the context of studies devoted to the reactivity of tin precursors towards carbon dioxide, at atmospheric pressure or under pressure, thus highlighting the suitable disposition of Sn to fix CO2. In the frame of a second part, the present review carries on to explore CO2 derivatives of molecular tin compounds by describing successively the complexes with carbamato, formato, and phosphinoformato ligands, and obtained from insertion reactions of carbon dioxide into Sn–X bonds (X = N, H, P, respectively). The last chapter is devoted to X-ray structures of transition metal/tin CO2 complexes exhibiting metallocarboxylato ligands. As in Part 1, for each tin compound reported and when described in the original study, the structural descriptions are supplemented by synthetic conditions and spectroscopic data.
      Citation: Inorganics
      PubDate: 2021-02-24
      DOI: 10.3390/inorganics9030018
      Issue No: Vol. 9, No. 3 (2021)
  • Inorganics, Vol. 9, Pages 19: Synthesis and Characterization of
           NaCd0.92Sn1.08, Na(Cd0.28Sn0.72)2 and Na2CdSn5 with Three-Dimensional
           Cd-Sn Frameworks

    • Authors: Yuki Asamiya, Takahiro Yamada, Hisanori Yamane
      First page: 19
      Abstract: The crystal structures of three new ternary compounds, NaCd0.92Sn1.08 (I), Na(Cd0.28Sn0.72)2 (II), and Na2CdSn5 (III) synthesized in a sodium-cadmium-tin system were determined by single-crystal X-ray analysis to be the following: (I) LiGeZn-type structure (hexagonal, a = 4.9326(1) Å, c = 10.8508(3) Å, space group P-6m2); (II) CaIn2-type structure (hexagonal, a = 4.8458(2) Å, c = 7.7569(3) Å, P63/mmc); and (III) isotype with tI-Na2ZnSn5 (tetragonal, a = 6.4248(1) Å, c = 22.7993(5) Å, I-42d). Each compound has a three-dimensional framework structure mainly composed of four-fold coordinated Cd and Sn atoms with Na atoms located in the framework space. Elucidation of the electrical properties of the polycrystalline samples indicated that compounds (I) and (II) are polar intermetallics with metallic conductivity, and compound (III) is a semiconducting Zintl compound. These properties were consistent with the electronic structures calculated using the ordered structure models of the compounds.
      Citation: Inorganics
      PubDate: 2021-03-06
      DOI: 10.3390/inorganics9030019
      Issue No: Vol. 9, No. 3 (2021)
  • Inorganics, Vol. 9, Pages 20: Photoluminescent Coordination Polymers Based
           on Group 12 Metals and 1H-Indazole-6-Carboxylic Acid

    • Authors: Antonio A. García-Valdivia, Estitxu Echenique-Errandonea, Gloria B. Ramírez-Rodríguez, José M. Delgado-López, Belén Fernández, Sara Rojas, Javier Cepeda, Antonio Rodríguez-Diéguez
      First page: 20
      Abstract: Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds.
      Citation: Inorganics
      PubDate: 2021-03-22
      DOI: 10.3390/inorganics9030020
      Issue No: Vol. 9, No. 3 (2021)
  • Inorganics, Vol. 9, Pages 9: Synthesis, Crystal Structure, Spectroscopic
           Characterization, DFT Calculations and Cytotoxicity Assays of a New Cu(II)
           Complex with an Acylhydrazone Ligand Derived from Thiophene

    • Authors: María R. Rodríguez, Lucía M. Balsa, Oscar E. Piro, Gustavo A. Etcheverría, Javier García-Tojal, Reinaldo Pis-Diez, Ignacio E. León, Beatriz P. Parajón-Costa, Ana C. González-Baró
      First page: 9
      Abstract: A new Cu(II) complex is synthetized by the reaction of copper nitrate and a N-acylhydrazone ligand obtained from the condensation of o-vanillin and 2-thiophecarbohydrazide (H2L). The solid-state structure of [Cu(HL)(H2O)](NO3)·H2O, or CuHL for simplicity, was determined by X-ray diffraction. In the cationic complex, the copper center is in a nearly squared planar environment with the nitrate interacting as a counterion. CuHL was characterized by spectroscopic techniques, including solid-state FTIR, Raman, electron paramagnetic resonance (EPR) and diffuse reflectance and solution UV-Vis electronic spectroscopy. Calculations based on the density functional theory (DFT) assisted the interpretation and assignment of the spectroscopic data. The complex does not show relevant antioxidant activity evaluated by the radical cation of 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) method, being even less active than the free ligand as a radical quencher. Cytotoxicity assays of CuHL against three human tumor cell lines, namely MG-63, A549 and HT-29, revealed an important enhancement of the effectiveness as compared with both the ligand and the free metal ion. Moreover, its cytotoxic effect was remarkably stronger than that of the reference metallodrug cisplatin in all cancer cell lines tested, a promissory result in the search for new metallodrugs of essential transition metals.
      Citation: Inorganics
      PubDate: 2021-01-20
      DOI: 10.3390/inorganics9020009
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 10: Molecular S = 2 High-Spin, S = 0 Low-Spin
           and S = 0 ⇄ 2 Spin-Transition/-Crossover Nickel(II)-Bis(nitroxide)
           Coordination Compounds

    • Authors: Takayuki Ishida, Saki Ito, Yuta Homma, Yukiya Kyoden
      First page: 10
      Abstract: Heterospin systems have a great advantage in frontier orbital engineering since they utilize a wide diversity of paramagnetic chromophores and almost infinite combinations and mutual geometries. Strong exchange couplings are expected in 3d–2p heterospin compounds, where the nitroxide (aminoxyl) oxygen atom has a direct coordination bond with a nickel(II) ion. Complex formation of nickel(II) salts and tert-butyl 2-pyridyl nitroxides afforded a discrete 2p–3d–2p triad. Ferromagnetic coupling is favored when the magnetic orbitals, nickel(II) dσ and radical π*, are arranged in a strictly orthogonal fashion, namely, a planar coordination structure is characterized. In contrast, a severe twist around the coordination bond gives an orbital overlap, resulting in antiferromagnetic coupling. Non-chelatable nitroxide ligands are available for highly twisted and practically diamagnetic complexes. Here, the Ni–O–N–Csp2 torsion (dihedral) angle is supposed to be a useful metric to describe the nickel ion dislocated out of the radical π* nodal plane. Spin-transition complexes exhibited a planar coordination structure in a high-temperature phase and a nonplanar structure in a low-temperature phase. The gradual spin transition is described as a spin equilibrium obeying the van’t Hoff law. Density functional theory calculation indicates that the energy level crossing of the high- and low-spin states. The optimized structures of diamagnetic and high-spin states well agreed with the experimental large and small torsions, respectively. The novel mechanism of the present spin transition lies in the ferro-/antiferromagnetic coupling switch. The entropy-driven mechanism is plausible after combining the results of the related copper(II)-nitroxide compounds. Attention must be paid to the coupling parameter J as a variable of temperature in the magnetic analysis of such spin-transition materials. For future work, the exchange coupling may be tuned by chemical modification and external stimulus, because it has been clarified that the parameter is sensitive to the coordination structure and actually varies from 2J/kB = +400 K to −1400 K.
      Citation: Inorganics
      PubDate: 2021-01-20
      DOI: 10.3390/inorganics9020010
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 11: Synthesis and Physical Properties of
           Tetrathiafulvalene-8-Quinolinato Zinc(II) and Nickel(II) Complexes

    • Authors: Keijiro Tsujimoto, Shinya Yamamoto, Hideki Fujiwara
      First page: 11
      Abstract: To develop donor–acceptor–donor (D–A–D) type new photo-electric conversion materials, new tetrathiafulvalene (TTF)-Mq2-TTF complexes 1 and 2 were synthesized, where two bis(n-hexylthio)tetrathiafulvalene moieties were attached to the Mq2 part (1: M = Zn, 2: M = Ni, q = 8-quinolinato) through amide bonds. UV-Vis absorption spectra of these complexes showed strong and sharp absorption maxima at 268 nm and small absorption maxima around 410 nm, corresponding to those of Znq2 and Niq2 parts. Furthermore, complexes 1 and 2 exhibited absorption tails up to a much longer wavelength region of ca. 700 nm, suggesting the appearance of charge transfer absorption from TTF to the Mq2 parts. The photoelectrochemical measurements on the thin films of these complexes casted on ITO-coated glass substrates suggest that positive photocurrents can be generated by the photoinduced intramolecular electron transfer process between the TTF and Mq2 parts.
      Citation: Inorganics
      PubDate: 2021-02-01
      DOI: 10.3390/inorganics9020011
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 12: Copper(II) Complexes with Tetradentate
           Piperazine-Based Ligands: DNA Cleavage and Cytotoxicity

    • Authors: Sebastian Doniz Kettenmann, Yvonne Nossol, Febee R. Louka, Julia R. Legrande, Elise Marine, Roland C. Fischer, Franz A. Mautner, Vinja Hergl, Nora Kulak, Salah S. Massoud
      First page: 12
      Abstract: Five-coordinate Cu(II) complexes, [Cu(Ln)X]ClO4/PF6, where Ln = piperazine ligands bearing two pyridyl arms and X = ClO4− for Ln = L1 (1-ClO4), L2 (2-ClO4), L3 (3-ClO4), and L6 (6-ClO4) as well as [Cu(Ln)Cl]PF6 for Ln = L1 (1-Cl), L4 (4-Cl), and L5 (5-Cl) have been synthesized and characterized by spectroscopic techniques. The molecular structures of the last two complexes were determined by X-ray crystallography. In aqueous acetonitrile solutions, molar conductivity measurements and UV-VIS spectrophotometric titrations of the complexes revealed the hydrolysis of the complexes to [Cu(Ln)(H2O)]2+ species. The biological activity of the Cu(II) complexes with respect to DNA cleavage and cytotoxicity was investigated. At micromolar concentration within 2 h and pH 7.4, DNA cleavage rate decreased in the order: 1-Cl ≈ 1-ClO4 > 3-ClO4 ≥ 2-ClO4 with cleavage enhancements of up to 23 million. Complexes 4-Cl, 5-Cl, and 6-ClO4 were inactive. In order to elucidate the cleavage mechanism, the cleavage of bis(4-nitrophenyl)phosphate (BNPP) and reactive oxygen species (ROS) quenching studies were conducted. The mechanistic pathway of DNA cleavage depends on the ligand’s skeleton: while an oxidative pathway was preferable for 1-Cl/1-ClO4, DNA cleavage by 2-ClO4 and 3-ClO4 predominantly proceeds via a hydrolytic mechanism. Complexes 1-ClO4, 3-ClO4, and 5-Cl were found to be cytotoxic against A2780 cells (IC50 30–40 µM). In fibroblasts, the IC50 value was much higher for 3-ClO4 with no toxic effect.
      Citation: Inorganics
      PubDate: 2021-02-01
      DOI: 10.3390/inorganics9020012
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 13: Non-Covalent Interactions of the Lewis Acids
           Cu–X, Ag–X, and Au–X (X = F and Cl) with Nine Simple Lewis Bases B:
           A Systematic Investigation of Coinage–Metal Bonds by Ab Initio

    • Authors: Ibon Alkorta, Nicholas R. Walker, Anthony C. Legon
      First page: 13
      Abstract: The equilibrium geometry and two measures (the equilibrium dissociation energy in the complete basis set limit, De(CBS) and the intermolecular stretching force constant kσ) of the strength of the non-covalent interaction of each of six Lewis acids M–X (M = Cu, Ag, Au) with each of nine simple Lewis bases B (B = N2, CO, HCCH, CH2CH2, H2S, PH3, HCN, H2O, and NH3) have been calculated at the CCSD(T)/aug-cc-pVTZ level of theory in a systematic investigation of the coinage–metal bond. Unlike the corresponding series of hydrogen-bonded B⋯HX and halogen-bonded B⋯XY complexes (and other series involving non-covalent interactions), De is not directly proportional to kσ. Nevertheless, as for the other series, it has been possible to express De in terms of the equation De = cNB.EMX, where NB and EMX are the nucleophilicities of the Lewis bases B and the electrophilicities of the Lewis acids M–X, respectively. The order of the EMX is determined to be EAuF > EAuCl > ECuF > ECuCl > EAgF ≈ EAgCl. A reduced electrophilicity defined as (EMX/σmax) is introduced, where σmax is the maximum positive value of the molecular electrostatic surface potential on the 0.001 e/bohr3 iso-surface. This quantity is, in good approximation, independent of whether F or Cl is attached to M.
      Citation: Inorganics
      PubDate: 2021-02-01
      DOI: 10.3390/inorganics9020013
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 14: Fluorination Effects in XPhos Gold(I)

    • Authors: Guillermo Moreno-Alcántar, Cristian Díaz-Rosas, Alberto Fernández-Alarcón, Luis Turcio-García, Marcos Flores-Álamo, Tomás Rocha-Rinza, Hugo Torrens
      First page: 14
      Abstract: Gold phosphine derivatives such as thiolates have been recently proposed as catalysts or catalyst precursors. The relevance of the supramolecular environment on the fine-tuning of the catalytical activity on these compounds incentivizes the use of tools that are convenient to characterize in detail the non-covalent landscape of the systems. Herein, we show the molecular and supramolecular diversity caused by the changes in the fluorination pattern in a family of new XPhos goldfluorothiolate derivatives. Furthermore, we studied the supramolecular interactions around the Au centers using quantum chemical topology tools, in particular the quantum theory of atoms in molecules (QTAIM) and the non-covalent interaction index. Our results give detailed insights into the fluorination effects on the strength of intramolecular and intermolecular interactions in these systems. We have also used QTAIM delocalization indexes to define a novel hapticity indicator. Finally, we assessed the trans influence of the fluorothiolates on the phosphine in terms of the change in the δ 31P-NMR. These results show the feasibility of the use of fluorination in the modulation of the electronic properties of Buchwald phosphine gold(I) compounds, and thereby its potential catalytic activity.
      Citation: Inorganics
      PubDate: 2021-02-02
      DOI: 10.3390/inorganics9020014
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 15: Accessing Low-Valent Titanium CCC-NHC
           Complexes: Toward Nitrogen Fixation

    • Authors: Sriloy Dey, T. Keith Hollis
      First page: 15
      Abstract: The dramatic expansion of the earth’s population can be directly correlated with the Haber–Bosch process for nitrogen fixation becoming widely available after World War II. The ready availability of artificial fertilizer derived thereof dramatically improved food supplies world-wide. Recently, artificial nitrogen fixation surpassed the natural process. The Haber–Bosch process is extremely energy and green-house gas intensive due to its high-temperature and H2 demands. Many low valent Ti(II) complexes of N2 are known. We report herein a preliminary investigation of the low-valent chemistry of Ti with the CCC-NHC ligand architecture. These CCC-NHC pincer Ti(IV) complexes are readily reduced with KC8 or Mg powder. Preliminary results indicate very different reactivity patterns with alkynes and phosphines for this ligand architecture versus prior ligands. Successful reduction to an intact low-valent (CCC-NHC)Ti complex was confirmed by re-oxidation with PhICl2.
      Citation: Inorganics
      PubDate: 2021-02-08
      DOI: 10.3390/inorganics9020015
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 16: The Photochemistry of
           Fe2(S2C3H6)(CO)6(µ-CO) and Its Oxidized Form, Two Simple
           [FeFe]-Hydrogenase CO-Inhibited Models. A DFT and TDDFT Investigation

    • Authors: Federica Arrigoni, Giuseppe Zampella, Luca De Gioia, Claudio Greco, Luca Bertini
      First page: 16
      Abstract: FeIFeI Fe2(S2C3H6)(CO)6(µ-CO) (1a–CO) and its FeIFeII cationic species (2a+–CO) are the simplest model of the CO-inhibited [FeFe] hydrogenase active site, which is known to undergo CO photolysis within a temperature-dependent process whose products and mechanism are still a matter of debate. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT) computations, the ground state and low-lying excited-state potential energy surfaces (PESs) of 1a–CO and 2a+–CO have been explored aimed at elucidating the dynamics of the CO photolysis yielding Fe2(S2C3H6)(CO)6 (1a) and [Fe2(S2C3H6)(CO)6]+ (2a+), two simple models of the catalytic site of the enzyme. Two main results came out from these investigations. First, a–CO and 2a+–CO are both bound with respect to any CO dissociation with the lowest free energy barriers around 10 kcal mol−1, suggesting that at least 2a+–CO may be synthesized. Second, focusing on the cationic form, we found at least two clear excited-state channels along the PESs of 2a+–CO that are unbound with respect to equatorial CO dissociation.
      Citation: Inorganics
      PubDate: 2021-02-09
      DOI: 10.3390/inorganics9020016
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 17: Misinterpretations in Evaluating
           Interactions of Vanadium Complexes with Proteins and Other Biological

    • Authors: João Costa Pessoa, Isabel Correia
      First page: 17
      Abstract: In aqueous media, VIV- and VV-ions and compounds undergo chemical changes such as hydrolysis, ligand exchange and redox reactions that depend on pH and concentration of the vanadium species, and on the nature of the several components present. In particular, the behaviour of vanadium compounds in biological fluids depends on their environment and on concentration of the many potential ligands present. However, when reporting the biological action of a particular complex, often the possibility of chemical changes occurring has been neglected, and the modifications of the complex added are not taken into account. In this work, we highlight that as soon as most vanadium(IV) and vanadium(V) compounds are dissolved in a biological media, they undergo several types of chemical transformations, and these changes are particularly extensive at the low concentrations normally used in biological experiments. We also emphasize that in case of a biochemical interaction or effect, to determine binding constants or the active species and/or propose mechanisms of action, it is essential to evaluate its speciation in the media where it is acting. This is because the vanadium complex no longer exists in its initial form.
      Citation: Inorganics
      PubDate: 2021-02-09
      DOI: 10.3390/inorganics9020017
      Issue No: Vol. 9, No. 2 (2021)
  • Inorganics, Vol. 9, Pages 73: Vanadium(V) Complexes with Siderophore
           Vitamin E-Hydroxylamino-Triazine Ligands

    • Authors: Maria Loizou, Ioanna Hadjiadamou, Chryssoula Drouza, Anastasios D. Keramidas, Yannis V. Simos, Dimitrios Peschos
      First page: 73
      Abstract: Novel vitamin E chelate siderophore derivatives and their VV and FeIII complexes have been synthesised and the chemical and biological properties have been evaluated. In particular, the α- and δ-tocopherol derivatives with bis-methyldroxylamino triazine (α-tocTHMA) and (δ-tocDPA) as well their VV complexes, [V2VO3(α-tocTHMA)2] and [V2IVO3(δ-tocTHMA)2], have been synthesised and characterised by infrared (IR), nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and ultra violet-visible (UV-Vis) spectroscopies. The dimeric vanadium complexes in solution are in equilibrium with their respefrctive monomers, H2O + [V2VO2(μ-O)]4+ = 2 [VVO(OH)]2+. The two amphiphilic vanadium complexes exhibit enhanced hydrolytic stability. EPR shows that the complexes in lipophilic matrix are mild radical initiators. Evaluation of their biological activity shows that the compounds do not exhibit any significant cytotoxicity to cells.
      Citation: Inorganics
      PubDate: 2021-09-29
      DOI: 10.3390/inorganics9100073
      Issue No: Vol. 9, No. 10 (2021)
  • Inorganics, Vol. 9, Pages 74: Diverse Coordination Numbers and Geometries
           in Pyridyl Adducts of Lanthanide(III) Complexes Based on β-Diketonate

    • Authors: Franz A. Mautner, Florian Bierbaumer, Roland C. Fischer, Ana Torvisco, Ramon Vicente, Mercè Font-Bardía, Ànnia Tubau, Saskia Speed, Salah S. Massoud
      First page: 74
      Abstract: Ten mononuclear rare earth complexes of formula [La(btfa)3(H2O)2] (1), [La(btfa)3(4,4′-Mt2bipy)] (2), [La(btfa)3(4,4′-Me2bipy)2] (3), [La(btfa)3(5,5′-Me2bipy)2] (4), [La(btfa)3(terpy)] (5), [La(btfa)3(phen)(EtOH)] (6), [La(btfa)3(4,4′-Me2bipy)(EtOH)] (7), [La(btfa)3(2-benzpy)(MeOH)] (8), [Tb(btfa)3(4,4′-Me2bipy)] (9) and (Hpy)[Eu(btfa)4] (10), where btfa = 4,4,4-trifuoro-1-phenylbutane-1,3-dionato anion, 4,4′-Mt2bipy = 4,4′-dimethoxy-2,2′-bipyridine, 4,4′-Me2bipy = 4,4′-dimethyl-2,2′-bipyridine, 5,5′-Me2bipy = 5,5′-dimethyl-2,2′-bipyridine, terpy = 2,2′:6′,2′-terpyridine, phen = 1,10-phenathroline, 2-benzpy = 2-(2-pyridyl)benzimidazole, Hpy = pyridiniumH+ cation) have been synthesized and structurally characterized. The complexes display coordination numbers (CN) eight for 1, 2, 9, 10, nine for 5, 6, 7, 8 and ten for 3 and 4. The solid-state luminescence spectra of Tb-9 and Eu-10 complexes showed the same characteristic bands predicted from the Tb(III) and Eu(III) ions. The Overall Quantum Yield measured (ϕTOT) at the excitation wavelength of 371 nm for both compounds yielded 1.04% for 9 and up to 34.56% for 10.
      Citation: Inorganics
      PubDate: 2021-09-30
      DOI: 10.3390/inorganics9100074
      Issue No: Vol. 9, No. 10 (2021)
  • Inorganics, Vol. 9, Pages 75: Facile Synthesis and Redox Behavior of an
           Overcrowded Spirogermabifluorene

    • Authors: Shogo Morisako, Kohsuke Noro, Takahiro Sasamori
      First page: 75
      Abstract: A spirogermabifluorene that bears sterically demanding 3,3′,5,5′-tetra(t-butyl)-2,2′-biphenylene groups (1) was obtained from the reaction of in-situ-generated 2,2′-dilithiobiphenylene with GeCl2·(dioxane). The solid-state structure and the redox behavior of 1 were examined by single-crystal X-ray diffraction analysis and electrochemical measurements, respectively. The sterically hindered biphenyl ligands endow 1 with high redox stability and increased electron affinity. The experimental observations were corroborated by theoretical DFT calculations.
      Citation: Inorganics
      PubDate: 2021-10-06
      DOI: 10.3390/inorganics9100075
      Issue No: Vol. 9, No. 10 (2021)
  • Inorganics, Vol. 9, Pages 76: Synthesis of N,O-Chelating
           Hydrazidopalladium Complexes from 1,2-Bis(trifluoroacetyl)hydrazine

    • Authors: Kayaki, Hayakawa, Ikariya
      First page: 76
      Abstract: N,O-chelating dicarbonylhydrazido-palladium complexes were synthesized by treatment of 1,2-bis(trifluoroacetyl)hydrazine with a mixture of a Pd(0) source, [Pd(dba)2] (DBA = dibenzylideneacetone), and four-electron donors including 1,3-bis(diphenylphosphino)propane (DPPP), N,N,N’,N’-tetramethylethylenediamine (TMEDA), and two equivalents of triphenylphosphine. The same products from DPPP and TMEDA could be obtained alternatively by using Pd(OAc)2 through deprotonation of the diacylhydrazine. The five-membered chelate structure was confirmed by NMR spectra and X-ray crystal structure determination. The X-ray structures indicate that the products are formally considered as Pd(II) complexes with a hydrazido(2–) ligand. In the case of the triphenylphosphine-coordinated complex, a fluxional behavior in dichloromethane-d2 was observed by variable temperature NMR experiments, possibly due to structural changes between the square planar and pseudo-tetrahedral geometries.
      Citation: Inorganics
      PubDate: 2021-10-07
      DOI: 10.3390/inorganics9100076
      Issue No: Vol. 9, No. 10 (2021)
  • Inorganics, Vol. 9, Pages 77: Nanostructure and Luminescent Properties of
           Bimetallic Lanthanide Eu/Gd, Tb/Gd and Eu/Tb Coordination Polymers

    • Authors: Helena Brunckova, Erika Mudra, Lucas Rocha, Eduardo Nassar, Willian Nascimento, Hristo Kolev, Maksym Lisnichuk, Alexandra Kovalcikova, Zuzana Molcanova, Magdalena Strečkova, Lubomir Medvecky
      First page: 77
      Abstract: This study presents the synthesis, structural and luminescence properties for lanthanide metal–organic frameworks (LnMOFs), which belong to the sub-class of coordination polymers. The series of nanosized LnMOFs (Ln = Eu, Gd, Tb, Eu0.5Gd0.5, Tb0.5Gd0.5 and Eu0.5Tb0.5) was prepared by solvothermal synthesis using a modulator (sodium acetate). We investigated the various surface chemistry compositions of the isostructural LnMOFs with a [Ln(btc)] structure (BTC: Benzene-1,3,5-tricarboxylate) by X-ray photoelectron spectroscopy (XPS). The XPS confirmed the mixed-valent Eu3+ and Eu2+ compounds, and the presence of Tb in both +3 and +4 valence states, and one +3 valency of Gd. A nanostructure of mixed LnMOFs (EuGd, TbGd and EuTb) with a rod-like shape is related to luminescence properties. The MOFs (EuTb and EuGd) presented Comission Internationale de l’Éclairage (CIE) chromaticities of x = 0.666 and y = 0.331, and x = 0.654 and y = 0.348, respectively, in the red region. They were better than the values desired for use in commercial phosphors, which are x = 0.64 and y = 0.35. For [Tb/Gd(btc)], the CIE coordinates were x = 0.334 and y = 0.562, presenting emissions in the green region. Bimetallic LnMOFs are very promising UV light sensors for biological applications.
      Citation: Inorganics
      PubDate: 2021-10-15
      DOI: 10.3390/inorganics9100077
      Issue No: Vol. 9, No. 10 (2021)
  • Inorganics, Vol. 9, Pages 2: Investigating the Factors Affecting the Ionic
           Conduction in Nanoconfined NaBH4

    • Authors: Xiaoxuan Luo, Aditya Rawal, Kondo-Francois Aguey-Zinsou
      First page: 2
      Abstract: Nanoconfinement is an effective strategy to tune the properties of the metal hydrides. It has been extensively employed to modify the ionic conductivity of LiBH4 as an electrolyte for Li-ion batteries. However, the approach does not seem to be applicable to other borohydrides such as NaBH4, which is found to reach a limited improvement in ionic conductivity of 10−7 S cm−1 at 115 °C upon nanoconfinement in Mobil Composition of Matter No. 41 (MCM-41) instead of 10−8 S cm−1. In comparison, introducing large cage anions in the form of Na2B12H12 naturally formed upon the nanoconfinement of NaBH4 was found to be more effective in leading to higher ionic conductivities of 10−4 S cm−1 at 110 °C.
      Citation: Inorganics
      PubDate: 2021-01-01
      DOI: 10.3390/inorganics9010002
      Issue No: Vol. 9, No. 1 (2021)
  • Inorganics, Vol. 9, Pages 3: Effect of Silane Functionalization on
           Properties of Poly(Lactic Acid)/Palygorskite Nanocomposites

    • Authors: Anton Kasprzhitskii, Georgy Lazorenko, Alexander Kruglikov, Irina Kuchkina, Vadim Gorodov
      First page: 3
      Abstract: Poly(lactic acid) (PLA)/palygorskite (Paly) nanocomposites were prepared using the melt compounding technique. Paly modified by 3-aminopropyltriethoxysilane (APTES) and vinyltrimethoxysilane (VTMS) was used as nanofiller for PLA with concentrations in the 1–7 wt% range. It has been found that the functionalization allows a covalent bond between the hydroxyl groups of the Paly and the PLA matrix, evidenced by the improvement in mechanical properties. Paly modification with VTMS has better properties compared with Pale modification with APTES. This indicates a better adhesion between the Paly-VTMS and PLA matrix, and a good dispersion of the nanofiller in the polymer matrix.
      Citation: Inorganics
      PubDate: 2021-01-02
      DOI: 10.3390/inorganics9010003
      Issue No: Vol. 9, No. 1 (2021)
  • Inorganics, Vol. 9, Pages 4: Influence of Substituents in Terephthalate
           Linker on the Structure of MOFs Obtained from Presynthesized
           Heterometallic Complex

    • Authors: Marina Barsukova, Evgeny Dudko, Denis Samsonenko, Konstantin Kovalenko, Alexey Ryadun, Aleksandr Sapianik, Vladimir Fedin
      First page: 4
      Abstract: The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic frameworks could be essential to solve the problem of tailored synthesis. In our study we use presynthesized heterometallic pivalate complex [Li2Zn2(piv)6(py)2] to obtain new MOFs with heterometallic core as a node of the framework. We are managed to obtain four new heterometallic MOFs: [H2N(CH3)2]2[Li2Zn2(bdc)4]·CH3CN·DMF (1), [Li2Zn2(H2Br2-bdc)(Br2-bdc)3]·2DMF (2), [H2N(CH3)2][LiZn2(ndc)3]·CH3CN (3) and [{Li2Zn2(dmf)(py)2}{LiZn(dmf)2}2 (NO2-bdc)6]·5DMF (4). Moreover three of them contain starting tetranuclear core {Li2Zn2} and saves its geometry. We also demonstrate the influence of substituent in terephthalate ring on preservation of tetranuclear core. For compound 1 it was shown that luminescence of the framework could be quenched when nitrobenzene is included in the pores.
      Citation: Inorganics
      PubDate: 2021-01-02
      DOI: 10.3390/inorganics9010004
      Issue No: Vol. 9, No. 1 (2021)
  • Inorganics, Vol. 9, Pages 5: Breast Cancer Stem Cell Active Copper(II)
           Complexes with Naphthol Schiff Base and Polypyridyl Ligands

    • Authors: Joshua Northcote-Smith, Alice Johnson, Kuldip Singh, Fabrizio Ortu, Kogularamanan Suntharalingam
      First page: 5
      Abstract: Breast cancer stem cells (CSCs) are a sub-population of tumour cells that can promote breast cancer relapse and metastasis. Current treatments are unable to completely remove breast CSCs, therefore it is essential to develop new chemotherapeutics that can remove breast CSCs at clinically compatible doses. Here we present the synthesis, characterisation, and anti-breast CSC properties of copper(II) complexes, [Cu(L2)(1,10-phenanthroline)]PF6 (2) and [Cu(L3)(1,10-phenanthroline)]PF6 (3) comprising of a tridentate (O,N,S) coordinated naphthol Schiff base ligand (L2 = (E)-1-(((2-(methylthio)ethyl)imino)methyl)naphthalen-2-ol or L3 = (E)-1-(((2-(ethylthio)ethyl)imino)methyl)naphthalen-2-ol and 1,10-phenanthroline. The copper(II) complexes (2 and 3) kill breast CSCs, cultured in monolayer and three-dimensional systems, in the micromolar range. Notably, 2 and 3 are more potent towards breast CSC mammospheres than salinomycin (up to 4.5-fold), an established anti-breast CSC agent. Further, cell-based studies indicate that 2 and 3 are readily taken up by breast CSCs and elevate intracellular reactive oxygen species (ROS) levels upon short exposure times (0.5–1 h). The latter is likely to be the underlying mechanism by which 2 and 3 induces breast CSC death.
      Citation: Inorganics
      PubDate: 2021-01-07
      DOI: 10.3390/inorganics9010005
      Issue No: Vol. 9, No. 1 (2021)
  • Inorganics, Vol. 9, Pages 6: Transition Metals in Catalysis: The
           Functional Relationship of Fe–S Clusters and Molybdenum or Tungsten
           Cofactor-Containing Enzyme Systems

    • Authors: Silke Leimkühler
      First page: 6
      Abstract: Following the “Molybdenum and Tungsten Enzyme conference—MoTEC2019” and the satellite meeting on “Iron–Sulfur for Life”, we wanted to emphasize the link between iron–sulfur clusters and their importance for the biosynthesis, assembly, and activity of complex metalloenzymes in this Special Issue of Inorganics, entitled “Transition Metals in Catalysis: The Functional Relationship of Fe–S Clusters and Molybdenum or Tungsten Cofactor-Containing Enzyme Systems” [...]
      Citation: Inorganics
      PubDate: 2021-01-13
      DOI: 10.3390/inorganics9010006
      Issue No: Vol. 9, No. 1 (2021)
  • Inorganics, Vol. 9, Pages 7: A Structural Survey of Poly-Functional
           Dithiocarbamate Ligands and the Aggregation Patterns They Sustain

    • Authors: See Mun Lee, Edward R. T. Tiekink
      First page: 7
      Abstract: An overview is presented of the crystal structures of transition metal, main group element, and lanthanide compounds containing poly-functional dithiocarbamate ligands, namely species containing two or more connected NCS2− residues. In all, there are 40 different ligands of this type that have been characterised crystallographically in their heavy-element compounds with up to six NCS2− residues; all are bridging. In most cases, the resulting aggregates are zero-dimensional, often di-nuclear, but aggregates of up to 36 metal (gold) atoms are noted. There are smaller numbers of one-, two-, and three-dimensional architectures sustained by poly-functional dithiocarbamate ligands in their respective crystals. The survey highlights the opportunities afforded by this generally under-studied class of ligand.
      Citation: Inorganics
      PubDate: 2021-01-15
      DOI: 10.3390/inorganics9010007
      Issue No: Vol. 9, No. 1 (2021)
  • Inorganics, Vol. 9, Pages 8: Acknowledgment to Reviewers of Inorganics in

    • Authors: Inorganics Editorial Office Inorganics Editorial Office
      First page: 8
      Abstract: Peer review is the driving force of journal development, and reviewers are gatekeepers who ensure that Inorganics maintains its standards for the high quality of its published papers [...]
      Citation: Inorganics
      PubDate: 2021-01-19
      DOI: 10.3390/inorganics9010008
      Issue No: Vol. 9, No. 1 (2021)
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