Special Issue "Cornerstones in Contemporary Inorganic Chemistry"

A special issue of Inorganics (ISSN 2304-6740).

Deadline for manuscript submissions: closed (31 March 2021).

Special Issue Editor

Prof. Dr. Duncan H. Gregory
E-Mail Website
Guest Editor
School of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, UK
Interests: nitrides; chalcogenides; carbides; hydrides; synthesis; structure; solid-state chemistry; materials chemistry
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Special Issue Information

Dear Colleagues,

This issue marks a key stage in the continued evolution of Inorganics as the go-to open access journal of cutting-edge inorganic chemistry. This Special Issue of Inorganics entitled “Cornerstones in Contemporary Inorganic Chemistry” will compile feature articles from some of the most influential and pioneering international leaders and rising lights in their respective areas of inorganic chemistry. This Special Issue will collate comprehensive and inspiring reviews and opinion pieces reflecting the current state of the art and projecting into the near and far horizons of all reaches of the discipline. The issue will provide instructive and stimulating articles that will be of lasting interest and relevance across both established and emerging fields of inorganic chemistry. “Cornerstones in Contemporary Inorganic Chemistry” will cover timely and important topics from among main group, d-block, and f-block molecular and coordination chemistry through supramolecular and organometallic chemistry to bioinorganic chemistry, inorganic medicinal chemistry, solid-state chemistry, and catalysis. These commentaries will act as references for the gamut of inorganic chemists from aspiring undergraduates to senior researchers and teachers.

Prof. Dr. Duncan Gregory
Guest Editor

Manuscript Submission Information

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Keywords

  • Review
  • Opinion piece
  • Tutorial
  • Primer
  • Concepts
  • Techniques
  • Synthesis
  • Structure
  • Bonding
  • Reactivity
  • Activity
  • Chemical Properties
  • Physical Properties
  • Applications

Published Papers (7 papers)

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Research

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Open AccessArticle
Hydrothermal Synthesis and Structural Investigation of a Crystalline Uranyl Borosilicate
Inorganics 2021, 9(4), 25; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9040025 - 06 Apr 2021
Viewed by 175
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[(UO [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessArticle
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
Inorganics 2021, 9(2), 16; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9020016 - 09 Feb 2021
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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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessCommunication
Breast Cancer Stem Cell Active Copper(II) Complexes with Naphthol Schiff Base and Polypyridyl Ligands
Inorganics 2021, 9(1), 5; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010005 - 07 Jan 2021
Viewed by 644
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessArticle
A Thermodynamic Investigation of Ni on Thin-Film Titanates (ATiO3)
Inorganics 2020, 8(12), 69; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120069 - 11 Dec 2020
Viewed by 596
Abstract
Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite [...] Read more.
Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3/MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessArticle
CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns
Inorganics 2020, 8(12), 65; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120065 - 01 Dec 2020
Viewed by 487
Abstract
Isonicotine amide, picoline amide, pyrazine 2-amide, 2- and 4-amino benzamides and various CuII salts were used to target CuII complexes of these ligands alongside with 1D and 2D coordination polymers. Under the criterion of obtaining crystalline and single phased materials a [...] Read more.
Isonicotine amide, picoline amide, pyrazine 2-amide, 2- and 4-amino benzamides and various CuII salts were used to target CuII complexes of these ligands alongside with 1D and 2D coordination polymers. Under the criterion of obtaining crystalline and single phased materials a number of new compounds were reliably reproduced. Remarkably, for some of these compounds the ideal Cu:ligand ratio of the starting materials turned out to be very different from Cu:ligand ratio in the products. Crystal and molecular structures from single-crystal XRD were obtained for all new compounds; phase purity was checked using powder XRD. We observed exclusively the Oamide and not the NH2amide function binding to CuII. In most of the cases; this occurred in chelates with the second pyridine, pyrazine or aminophenyl N function. µ-O,N ditopic bridging was frequently observed for the N = pyridine, pyrazine or aminophenyl functions, but not exclusively. The geometry around CuII in these compounds was very often axially elongated octahedral or square pyramidal. X-band EPR spectra of powder samples revealed various spectral symmetry patterns ranging from axial over rhombic to inverse axial. Although the EPR spectra cannot be unequivocally correlated to the observed geometry of CuII in the solid state structures, the EPR patterns can help to support assumed structures as shown for the compound [Cu(Ina)2Br2] (Ina = isonicotine amide). As UV-vis absorption spectroscopy and magnetic measurement in the solid can also be roughly correlated to the surrounding of CuII, we suggest the combination of EPR, UV-vis spectroscopy and magnetic measurements to elucidate possible structures of CuII compounds with such ligands. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessCommunication
Silver Cyanoguanidine Nitrate Hydrate: Ag(C2N4H4)NO3·½ H2O, a Cyanoguanidine Compound Coordinating by an Inner Nitrogen Atom
Inorganics 2020, 8(12), 64; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120064 - 24 Nov 2020
Viewed by 568
Abstract
Silver(I) cyanoguanidine nitrate hydrate, Ag(C2N4H4)NO3·½H2O, was synthesized as the first cyanoguanidine solid-state complex in which monovalent Ag is coordinated through inner nitrogen N atoms. Its structure was characterized by single-crystal X-ray diffraction, crystallizing [...] Read more.
Silver(I) cyanoguanidine nitrate hydrate, Ag(C2N4H4)NO3·½H2O, was synthesized as the first cyanoguanidine solid-state complex in which monovalent Ag is coordinated through inner nitrogen N atoms. Its structure was characterized by single-crystal X-ray diffraction, crystallizing in the acentric orthorhombic space group P21212 with a = 10.670(3) Å, b = 18.236(5) Å, and c = 3.5078(9) Å. The differing chemical bondings of Ag(C2N4H4)NO3·½H2O and Ag(C2N4H4)3NO3 were compared on the basis of first-principle calculations. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Review

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Open AccessReview
Lanthanide-Based Single-Molecule Magnets Derived from Schiff Base Ligands of Salicylaldehyde Derivatives
Inorganics 2020, 8(12), 66; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics8120066 - 04 Dec 2020
Viewed by 638
Abstract
The breakthrough in Ln(III)-based SMMs with Schiff base ligands have been occurred for the last decade on account of their magnetic behavior, anisotropy and relaxation pathways. Herein, we review the synthetic strategy, from a structural point of view and magnetic properties of mono, [...] Read more.
The breakthrough in Ln(III)-based SMMs with Schiff base ligands have been occurred for the last decade on account of their magnetic behavior, anisotropy and relaxation pathways. Herein, we review the synthetic strategy, from a structural point of view and magnetic properties of mono, di, tri and polynuclear Ln(III)-based single-molecule magnets mainly with Schiff bases of Salicylaldehyde origin. Special attention has been given to some important breakthroughs that are changing the perspective of this field with a special emphasis on slow magnetic relaxation. An overview of 50 Ln(III)-Schiff base complexes with SMM behavior, covering the period 2008–2020, which have been critical in understanding the magnetic interactions between the Ln(III)-centers, are presented and discussed in detail. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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