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Inorganics
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Cornerstones in Contemporary Inorganic Chemistry
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Cornerstones in Contemporary Inorganic Chemistry

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

Deadline for manuscript submissions: closed (31 March 2022) | Viewed by 57362

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Prof. Dr. Duncan H. Gregory

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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
Special Issues, Collections and Topics in MDPI journals

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

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Keywords

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

Published Papers (19 papers)

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Editorial

Jump to: Research, Review

5 pages, 205 KiB  
Editorial
Cornerstones in Contemporary Inorganic Chemistry
by Duncan H. Gregory
Inorganics 2022, 10(8), 108; https://doi.org/10.3390/inorganics10080108 - 28 Jul 2022
Viewed by 1239
Abstract
I am very happy to be able to present this Special Issue of Inorganics [...] Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)

Research

Jump to: Editorial, Review

12 pages, 733 KiB  
Article
Synthesis, Structure and Bonding in Pentagonal Bipyramidal Cluster Compounds Containing a cyclo-Sn5 Ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo)
by Sourav Mondal, Wei-Xing Chen, Zhong-Ming Sun and John E. McGrady
Inorganics 2022, 10(6), 75; https://doi.org/10.3390/inorganics10060075 - 30 May 2022
Cited by 5 | Viewed by 3907
Abstract
In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)3CrSn5Cr(CO)3]4− and [(CO)3MoSn5Mo(CO)3]4−, both of which have a pentagonal bipyramidal core. The structures are [...] Read more.
In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)3CrSn5Cr(CO)3]4− and [(CO)3MoSn5Mo(CO)3]4−, both of which have a pentagonal bipyramidal core. The structures are similar to that of previously reported [(CO)3MoPb5Mo(CO)3]4− and our analysis of the bonding suggests that they are best formulated as containing Sn54− rings bridging two zerovalent M(CO)3 fragments. The electronic structure is compared to two isolobal M2E5 clusters, [CpCrP5CrCp]− and Tl77−, both of which show clear evidence for trans-annular bonds between the apical atoms that is not immediately obvious in the title clusters. Our analysis shows that the balance between E-E and M-M bonding is a delicate one, and shifts in the relative energies of the orbitals on the E5 and M2 fragments generate a continuum of bonding situations linked by the degree of localisation of the cluster LUMO. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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10 pages, 3256 KiB  
Article
Multivariate Linear Regression Models to Predict Monomer Poisoning Effect in Ethylene/Polar Monomer Copolymerization Catalyzed by Late Transition Metals
by Wei Zhao, Zhihao Liu, Yanan Zhao, Yi Luo and Shengbao He
Inorganics 2022, 10(2), 26; https://doi.org/10.3390/inorganics10020026 - 21 Feb 2022
Cited by 3 | Viewed by 2066
Abstract
This study combined density functional theory (DFT) calculations and multivariate linear regression (MLR) to analyze the monomer poisoning effect in ethylene/polar monomer copolymerization catalyzed by the Brookhart-type catalysts. The calculation results showed that the poisoning effect of polar monomers with relatively electron-deficient functional [...] Read more.
This study combined density functional theory (DFT) calculations and multivariate linear regression (MLR) to analyze the monomer poisoning effect in ethylene/polar monomer copolymerization catalyzed by the Brookhart-type catalysts. The calculation results showed that the poisoning effect of polar monomers with relatively electron-deficient functional groups is weaker, such as ethers, and halogens. On the contrary, polar monomers with electron-rich functional groups (carbonyl, carboxyl, and acyl groups) exert a stronger poisoning effect. In addition, three descriptors that significantly affect the poisoning effect have been proposed on the basis of the multiple linear regression model, viz., the chemical shift of the vinyl carbon atom and heteroatom of polar monomer as well as the metal-X distance in the σ-coordination structure. It is expected that these models could guide the development of efficient catalytic copolymerization system in this field. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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30 pages, 5812 KiB  
Article
Aqueous Solution Equilibria and Spectral Features of Copper Complexes with Tripeptides Containing Glycine or Sarcosine and Leucine or Phenylalanine
by Giselle M. Vicatos, Ahmed N. Hammouda, Radwan Alnajjar, Raffaele P. Bonomo, Gabriele Valora, Susan A. Bourne and Graham E. Jackson
Inorganics 2022, 10(1), 8; https://doi.org/10.3390/inorganics10010008 - 10 Jan 2022
Cited by 1 | Viewed by 3221
Abstract
Copper(II) complexes of glycyl-L-leucyl-L-histidine (GLH), sarcosyl-L-leucyl-L-histidine (Sar-LH), glycyl-L-phenylalanyl-L-histidine (GFH) and sarcosyl-L-phenylalanyl-L-histidine (Sar-FH) have potential anti-inflammatory activity, which can help to alleviate the symptoms associated with rheumatoid arthritis (RA). From pH 2–11, the MLH, ML, MLH-1 and MLH-2 species formed. The combination [...] Read more.
Copper(II) complexes of glycyl-L-leucyl-L-histidine (GLH), sarcosyl-L-leucyl-L-histidine (Sar-LH), glycyl-L-phenylalanyl-L-histidine (GFH) and sarcosyl-L-phenylalanyl-L-histidine (Sar-FH) have potential anti-inflammatory activity, which can help to alleviate the symptoms associated with rheumatoid arthritis (RA). From pH 2–11, the MLH, ML, MLH-1 and MLH-2 species formed. The combination of species for each ligand was different, except at the physiological pH, where CuLH-2 predominated for all ligands. The prevalence of this species was supported by EPR, ultraviolet-visible spectrophotometry, and mass spectrometry, which suggested a square planar CuN4 coordination. All ligands have the same basicity for the amine and imidazole-N, but the methyl group of sarcosine decreased the stability of MLH and MLH-2 by 0.1–0.34 and 0.46–0.48 log units, respectively. Phenylalanine increased the stability of MLH and MLH-2 by 0.05–0.29 and 1.19–1.21 log units, respectively. For all ligands, 1H NMR identified two coordination modes for MLH, where copper(II) coordinates via the amine-N and neighboring carbonyl-O, as well as via the imidazole-N and carboxyl-O. EPR spectroscopy identified the MLH, ML and MLH-2 species for Cu-Sar-LH and suggested a CuN2O2 chromophore for ML. DFT calculations with water as a solvent confirmed the proposed coordination modes of each species at the B3LYP level combined with 6-31++G**. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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13 pages, 6409 KiB  
Article
Novel Fluoridoaluminates from Ammonothermal Synthesis: Two Modifications of K2AlF5 and the Elpasolite Rb2KAlF6
by Christian Bäucker, Peter Becker, Keshia J. Morell and Rainer Niewa
Inorganics 2022, 10(1), 7; https://doi.org/10.3390/inorganics10010007 - 10 Jan 2022
Cited by 3 | Viewed by 1903
Abstract
Two new modifications of the pentafluoridoaluminate K2AlF5 were obtained from ammonothermal synthesis at 753 K, 224 MPa and 773 K, 220 MPa, respectively. Both crystallize in the orthorhombic space group type Pbcn, with close metric relations and feature kinked [...] Read more.
Two new modifications of the pentafluoridoaluminate K2AlF5 were obtained from ammonothermal synthesis at 753 K, 224 MPa and 773 K, 220 MPa, respectively. Both crystallize in the orthorhombic space group type Pbcn, with close metric relations and feature kinked chains of cis-vertex-connected AlF6 octahedra resulting in the Niggli formula ∞1{[AlF2/2eF4/1t]2−}. The differences lie in the number of octahedra necessary for repetition within the chains, which for K2AlF5-2 is realized after four and for K2AlF5-3 after eight octahedra. As a result, the orthorhombic unit cell for K2AlF5-3 is doubled in chain prolongation direction [001] as compared to K2AlF5-2 (1971.18(4) pm versus 988.45(3) pm, respectively), while the unit cell parameters within the other two directions are virtually identical. Moreover, the new elpasolite Rb2KAlF6 is reported, crystallizing in the cubic space group Fm3¯m with a = 868.9(1) pm and obtained under ammonothermal conditions at 723 K and 152 MPa. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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15 pages, 2687 KiB  
Article
Functionalized Tris(anilido)triazacyclononanes as Hexadentate Ligands for the Encapsulation of U(III), U(IV) and La(III) Cations
by Alasdair Formanuik, Fabrizio Ortu, Iñigo J. Vitorica-Yrezabal, Floriana Tuna, Eric J. L. McInnes, Louise S. Natrajan and David P. Mills
Inorganics 2021, 9(12), 86; https://doi.org/10.3390/inorganics9120086 - 28 Nov 2021
Cited by 3 | Viewed by 2332
Abstract
Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we [...] Read more.
Tripodal multidentate ligands have become increasingly popular in f-element chemistry for stabilizing unusual bonding motifs and supporting small molecule activation processes. The steric and electronic effects of ligand donor atom substituents have proved crucial in both of these applications. In this study we functionalized the previously reported tris-anilide ligand {tacn(SiMe2NPh)3} (tacn = 1,3,7-triazacyclononane) to incorporate substituted aromatic rings, with the aim of modifying f-element complex solubility and ligand steric effects. We report the synthesis of two proligands, {tacn(SiMe2NHAr)3} (Ar = C6H3Me2-3,5 or C6H4Me-4), and their respective group 1 transfer agents—{tacn(SiMe2NKAr)3}, M(III) complexes [M{tacn(SiMe2NAr)3}] for M = La and U, and U(IV) complexes [M{tacn(SiMe2NAr)3}(Cl)]. These compounds were characterized by multinuclear NMR and FTIR spectroscopy and elemental analysis. The paramagnetic uranium complexes were also characterized by solid state magnetic measurements and UV/Vis/NIR spectroscopy. U(III) complexes were additionally studied by EPR spectroscopy. The solid state structures of all f-block complexes were authenticated by single-crystal X-ray diffraction (XRD), together with a minor byproduct [U{tacn(SiMe2NC6H4Me-4)3}(I)]. Comparisons of the characterization data of our f-element complexes with similar literature examples containing the {tacn(SiMe2NPh)3} ligand set showed minor changes in physicochemical properties resulting from the different aromatic ring substitution patterns we investigated. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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9 pages, 1416 KiB  
Article
Synthesis and Characterization of Super Bulky β-Diketiminato Group 1 Metal Complexes
by Dafydd D. L. Jones, Samuel Watts and Cameron Jones
Inorganics 2021, 9(9), 72; https://doi.org/10.3390/inorganics9090072 - 16 Sep 2021
Cited by 7 | Viewed by 3653
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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20 pages, 5598 KiB  
Article
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)
by Giacomo Manfroni, Simona S. Capomolla, Alessandro Prescimone, Edwin C. Constable and Catherine E. Housecroft
Inorganics 2021, 9(7), 54; https://doi.org/10.3390/inorganics9070054 - 10 Jul 2021
Cited by 7 | Viewed by 2573
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) [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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9 pages, 2067 KiB  
Article
Synthesis and Characterisation of Molecular Polarised-Covalent Thorium-Rhenium and -Ruthenium Bonds
by Joseph P. A. Ostrowski, Ashley J. Wooles and Stephen T. Liddle
Inorganics 2021, 9(5), 30; https://doi.org/10.3390/inorganics9050030 - 21 Apr 2021
Cited by 8 | Viewed by 2441
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-C [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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14 pages, 2325 KiB  
Article
Hydrothermal Synthesis and Structural Investigation of a Crystalline Uranyl Borosilicate
by Kristen A. Pace, Vladislav V. Klepov, Mark D. Smith, Travis Williams, Gregory Morrison, Jochen A. Lauterbach, Scott T. Misture and Hans-Conrad zur Loye
Inorganics 2021, 9(4), 25; https://doi.org/10.3390/inorganics9040025 - 06 Apr 2021
Cited by 3 | Viewed by 2219
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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17 pages, 4134 KiB  
Article
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
by Federica Arrigoni, Giuseppe Zampella, Luca De Gioia, Claudio Greco and Luca Bertini
Inorganics 2021, 9(2), 16; https://doi.org/10.3390/inorganics9020016 - 09 Feb 2021
Cited by 4 | Viewed by 3039
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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13 pages, 1739 KiB  
Communication
Breast Cancer Stem Cell Active Copper(II) Complexes with Naphthol Schiff Base and Polypyridyl Ligands
by Joshua Northcote-Smith, Alice Johnson, Kuldip Singh, Fabrizio Ortu and Kogularamanan Suntharalingam
Inorganics 2021, 9(1), 5; https://doi.org/10.3390/inorganics9010005 - 07 Jan 2021
Cited by 7 | Viewed by 3033
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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13 pages, 5531 KiB  
Article
A Thermodynamic Investigation of Ni on Thin-Film Titanates (ATiO3)
by Chao Lin, Alexandre C. Foucher, Eric A. Stach and Raymond J. Gorte
Inorganics 2020, 8(12), 69; https://doi.org/10.3390/inorganics8120069 - 11 Dec 2020
Cited by 7 | Viewed by 2450
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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20 pages, 4533 KiB  
Article
CuII Complexes and Coordination Polymers with Pyridine or Pyrazine Amides and Amino Benzamides—Structures and EPR Patterns
by Ines Wackerbarth, Ni Nyoman Agnes Tri Widhyadnyani, Simon Schmitz, Kathrin Stirnat, Katharina Butsch, Ingo Pantenburg, Gerd Meyer and Axel Klein
Inorganics 2020, 8(12), 65; https://doi.org/10.3390/inorganics8120065 - 01 Dec 2020
Cited by 4 | Viewed by 2873
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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7 pages, 15959 KiB  
Communication
Silver Cyanoguanidine Nitrate Hydrate: Ag(C2N4H4)NO3·½ H2O, a Cyanoguanidine Compound Coordinating by an Inner Nitrogen Atom
by Xianji Qiao, Alex J. Corkett, Dongbao Luo and Richard Dronskowski
Inorganics 2020, 8(12), 64; https://doi.org/10.3390/inorganics8120064 - 24 Nov 2020
Cited by 3 | Viewed by 2407
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

Jump to: Editorial, Research

29 pages, 8813 KiB  
Review
Metal Organic Frameworks as Heterogeneous Catalysts in Olefin Epoxidation and Carbon Dioxide Cycloaddition
by Alessia Tombesi and Claudio Pettinari
Inorganics 2021, 9(11), 81; https://doi.org/10.3390/inorganics9110081 - 15 Nov 2021
Cited by 25 | Viewed by 4959
Abstract
Metal–organic frameworks (MOFs) are a family of porous crystalline materials that serve in some cases as versatile platforms for catalysis. In this review, we overview the recent developments about the use of these species as heterogeneous catalysts in olefin epoxidation and carbon dioxide [...] Read more.
Metal–organic frameworks (MOFs) are a family of porous crystalline materials that serve in some cases as versatile platforms for catalysis. In this review, we overview the recent developments about the use of these species as heterogeneous catalysts in olefin epoxidation and carbon dioxide cycloaddition. We report the most important results obtained in this field relating them to the presence of specific organic linkers, metal nodes or clusters and mixed-metal species. Recent advances obtained with MOF nanocomposites were also described. Finally we compare the results and summarize the major insights in specific Tables, outlining the major challenges for this emerging field. This work could promote new research aimed at producing coordination polymers and MOFs able to catalyse a broader range of CO2 consuming reactions. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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13 pages, 2374 KiB  
Review
Pyridinesilver Tetraoxometallate Complexes: Overview of the Synthesis, Structure, and Properties of Pyridine Complexed AgXO4 (X = Cl, Mn, Re) Compounds
by Fernanda Paiva Franguelli, Kende Attila Béres and Laszló Kótai
Inorganics 2021, 9(11), 79; https://doi.org/10.3390/inorganics9110079 - 30 Oct 2021
Cited by 11 | Viewed by 2579
Abstract
We reviewed the synthesis, structure, and properties of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) compounds with various compositions ([AgPy2] XO4, [AgPy2XO4]·0.5Py, [AgPy4] XO4, and 4 [AgPy [...] Read more.
We reviewed the synthesis, structure, and properties of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) compounds with various compositions ([AgPy2] XO4, [AgPy2XO4]·0.5Py, [AgPy4] XO4, and 4 [AgPy2XO4] [AgPy4] XO4). We also clarified the controversial information about the existence and composition of pyridine complexes of silver permanganate, used widely as mild and selective oxidants in organic chemistry. We discussed in detail the available structural and spectroscopic (IR, Raman, and UV) data and thermal behavior, including the existence and consequence of quasi-intramolecular reactions between the reducing ligand and anions containing oxygen. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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34 pages, 14929 KiB  
Review
Solvothermal Synthesis Routes to Substituted Cerium Dioxide Materials
by James W. Annis, Janet M. Fisher, David Thompsett and Richard I. Walton
Inorganics 2021, 9(6), 40; https://doi.org/10.3390/inorganics9060040 - 21 May 2021
Cited by 10 | Viewed by 4235
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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40 pages, 9236 KiB  
Review
Lanthanide-Based Single-Molecule Magnets Derived from Schiff Base Ligands of Salicylaldehyde Derivatives
by Mamo Gebrezgiabher, Yosef Bayeh, Tesfay Gebretsadik, Gebrehiwot Gebreslassie, Fikre Elemo, Madhu Thomas and Wolfgang Linert
Inorganics 2020, 8(12), 66; https://doi.org/10.3390/inorganics8120066 - 04 Dec 2020
Cited by 19 | Viewed by 3871
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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