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Inorganic Chemistry in Europe
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Inorganic Chemistry in Europe

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (31 December 2024) | Viewed by 5991

Special Issue Editor

Dr. Vassilis Tangoulis

E-Mail Website
Guest Editor
Department of Chemistry, University of Patras, Patra, Greece
Interests: hybrid carbon-based nano-materials; encapsulation/decoration of functionalized multi-wall nanotubes with single molecule magnets (SMMs) and the study of their magnetic behaviour; application of hybrid materials in the area of spintronics or medicine (MRI agents)
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Inorganic Chemistry is one of the most popular and fastest growing, interdisciplinary research fields of Chemistry, which is served by an appreciable number of faculty members and Research Directors in Universities and Research Institutes. The research interests of the Inorganic Chemistry community span the areas of synthetic inorganic chemistry (coordination clusters, polymers and MOFs), structural chemistry, materials science, spectroscopic, physicochemical and theoretical characterization, molecule-based magnetism, luminescence, catalysis, conductivity, bioinorganic and medicinal inorganic chemistry, and photochemistry, to name a few.

The present Special Issue is a compilation of novel, cutting-edge achievements in the most interesting areas of modern inorganic chemistry, which are as follows:

  • Single-molecule magnets, MOFs;
  • Spin crossover;
  • Multifunctional magnetic materials;
  • Magnetocaloric effect;
  • Crystal structure;
  • Structure−property relationships;
  • Magnetic relaxation;
  • Magnetic materials;
  • Prussian blue analogues and photomagnetism;
  • Inorganic heterostructures ;
  • Luminescence thermometers;
  • Inorganic dyes;
  • Bio-inorganic compounds;
  • Inorganic materials in catalysis;
  • Inorganic materials for supercapacitors.

This Special Issue will contain the most recent results obtained in research laboratories of prominent inorganic chemists from Europe working in the described broad area of inorganic chemistry. As such, this Special Issue will be interesting to other chemists working in this field and beyond—all those who further advance science and human knowledge.

Dr. Vassilis Tangoulis
Guest Editor

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Published Papers (5 papers)

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Research

24 pages, 4572 KiB  
Article
Heteroleptic Coumarin-Based Silver(I) Complexes: Possible New Antimicrobial Agents
by Erika Mooney, Brendan Twamley, Gordon Cooke, Emma Caraher, Matthias Tacke, Fintan Kelleher and Bernadette S. Creaven
Molecules 2024, 29(24), 5917; https://doi.org/10.3390/molecules29245917 - 15 Dec 2024
Cited by 1 | Viewed by 922
Abstract
Heteroleptic coumarin-based silver(I) complexes with improved solubility profiles were synthesised using either triphenylphosphine or an N-heterocyclic carbene as adduct ligands, and were fully characterised using IR and NMR spectroscopy, elemental analysis, and, where possible, X-ray crystallography. The triphenylphosphine adducts formed well-resolved structures, [...] Read more.
Heteroleptic coumarin-based silver(I) complexes with improved solubility profiles were synthesised using either triphenylphosphine or an N-heterocyclic carbene as adduct ligands, and were fully characterised using IR and NMR spectroscopy, elemental analysis, and, where possible, X-ray crystallography. The triphenylphosphine adducts formed well-resolved structures, where the oxyacetate ligands asymmetrically chelated the silver(I) ion in a bidentate chelating mode, and the silver(I) ion was also bound to two triphenylphosphine ligands. The solubility profile and photostability of the adducts were considerably improved compared to those of previously isolated simple coumarin silver(I) complexes. Analysis of the coumarin N-heterocyclic carbene(NHC) silver(I) adduct indicated that it likely formed as a complex aggregate species with an overall stoichiometry of 1:1:1 coumarin:Ag(I):NHC. The Kirby Bauer assay and broth microdilution assays were used to assess the silver(I) complexes’ and adducts’ antimicrobial activity against pathogenic strains of Pseudomonas aeruginosa, Escherichia coli, and MRSA. Interestingly, the formation of more soluble complexes did not increase the activity of the silver(I) complexes and, in effect, made them less effective antimicrobial agents, particularly against Escherichia coli and Pseudomonas aeruginosa, although they retained their activity against MRSA. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe)
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18 pages, 4439 KiB  
Article
Chelating Properties of N6O-Donors Toward Cu(II) Ions: Speciation in Aqueous Environments and Catalytic Activity of the Dinuclear Complexes
by Andrea Cendron, Martina Chianese, Kamil Zarzycki, Paolo Ruzza, Claudia Honisch, Justyna Brasuń and Mauro Carraro
Molecules 2024, 29(23), 5708; https://doi.org/10.3390/molecules29235708 - 3 Dec 2024
Viewed by 876
Abstract
This study focuses on the use of three isostructural N6O donor ligands, specifically known to form complexes with copper ions, to chelate Cu(II) from aqueous solutions. The corresponding Cu(II) complexes feature a dinuclear copper core mimicking the active site of natural [...] Read more.
This study focuses on the use of three isostructural N6O donor ligands, specifically known to form complexes with copper ions, to chelate Cu(II) from aqueous solutions. The corresponding Cu(II) complexes feature a dinuclear copper core mimicking the active site of natural superoxide dismutase (SOD) enzymes while also creating a coordination environment favorable for catalase (CAT) activity, being thus appealing as catalytic antioxidant systems. Given the critical role of copper dysregulation in the pathophysiology of Alzheimer’s disease (AD), these complexes may help mitigate the harmful effects of free Cu(II) ions: the goal is to transform copper’s reactive oxygen species (ROS)-generating properties into beneficial ROS-scavenging action. This study investigates the speciation, chelating efficiency, and metal selectivity of these ligands, as well as the antioxidant activity of the resulting complexes under aqueous and physiologically relevant conditions. Additionally, the ligands, equipped with functional groups for attaching targeting moieties, are conjugated with a small peptide that may act as an anti-aggregating agent of β-amyloid peptides, aiming to develop a multifunctional therapeutic strategy against Alzheimer’s disease. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe)
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16 pages, 4159 KiB  
Article
Effect of Substituted Pyridine Co-Ligands and (Diacetoxyiodo)benzene Oxidants on the Fe(III)-OIPh-Mediated Triphenylmethane Hydroxylation Reaction
by Patrik Török and József Kaizer
Molecules 2024, 29(16), 3842; https://doi.org/10.3390/molecules29163842 - 13 Aug 2024
Viewed by 1068
Abstract
Iodosilarene derivatives (PhIO, PhI(OAc)2) constitute an important class of oxygen atom transfer reagents in organic synthesis and are often used together with iron-based catalysts. Since the factors controlling the ability of iron centers to catalyze alkane hydroxylation are not yet fully [...] Read more.
Iodosilarene derivatives (PhIO, PhI(OAc)2) constitute an important class of oxygen atom transfer reagents in organic synthesis and are often used together with iron-based catalysts. Since the factors controlling the ability of iron centers to catalyze alkane hydroxylation are not yet fully understood, the aim of this report is to develop bioinspired non-heme iron catalysts in combination with PhI(OAc)2, which are suitable for performing C-H activation. Overall, this study provides insight into the iron-based ([FeII(PBI)3(CF3SO3)2] (1), where PBI = 2-(2-pyridyl)benzimidazole) catalytic and stoichiometric hydroxylation of triphenylmethane using PhI(OAc)2, highlighting the importance of reaction conditions including the effect of the co-ligands (para-substituted pyridines) and oxidants (para-substituted iodosylbenzene diacetates) on product yields and reaction kinetics. A number of mechanistic studies have been carried out on the mechanism of triphenylmethane hydroxylation, including C-H activation, supporting the reactive intermediate, and investigating the effects of equatorial co-ligands and coordinated oxidants. Strong evidence for the electrophilic nature of the reaction was observed based on competitive experiments, which included a Hammett correlation between the relative reaction rate (logkrel) and the σp (4R-Py and 4R’-PhI(OAc)2) parameters in both stoichiometric (ρ = +0.87 and +0.92) and catalytic (ρ = +0.97 and +0.77) reactions. The presence of [(PBI)2(4R-Py)FeIIIOIPh-4R’]3+ intermediates, as well as the effect of co-ligands and coordinated oxidants, was supported by their spectral (UV–visible) and redox properties. It has been proven that the electrophilic nature of iron(III)-iodozilarene complexes is crucial in the oxidation reaction of triphenylmethane. The hydroxylation rates showed a linear correlation with the FeIII/FeII redox potentials (in the range of −350 mV and −524 mV), which suggests that the Lewis acidity and redox properties of the metal centers greatly influence the reactivity of the reactive intermediates. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe)
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12 pages, 2990 KiB  
Article
Solid State and Solution Structures of Lanthanide Nitrate Complexes of Tris-(1-napthylphosphine oxide)
by Simon J. Coles, Laura J. McCormick McPherson, Andrew W. G. Platt and Kuldip Singh
Molecules 2024, 29(11), 2580; https://doi.org/10.3390/molecules29112580 - 30 May 2024
Cited by 1 | Viewed by 986
Abstract
Coordination complexes of lanthanide metals with tris-1-naphthylphosphine oxide (Nap3PO, L) have not been previously reported in the literature. We describe here the formation of lanthanide(III) nitrate complexes Ln(NO3)3L4 (Ln = Eu to Lu) and the structures [...] Read more.
Coordination complexes of lanthanide metals with tris-1-naphthylphosphine oxide (Nap3PO, L) have not been previously reported in the literature. We describe here the formation of lanthanide(III) nitrate complexes Ln(NO3)3L4 (Ln = Eu to Lu) and the structures of [Ln(NO3)3L2]·2L (Ln = Eu, Dy, Ho, Er) and L. The core structure of the complexes is an eight-coordinate [Ln(NO3)3L2] with the third and fourth ligands H-bonded via their oxygen atoms to one of the naphthyl rings. The structures are compared with those of the analogous complexes of triphenylphosphine oxide and show that the Ln-O(P) bond in the Nap3PO complexes is slightly longer than expected on the basis of differences in coordination numbers. The reaction solutions, investigated by 31P and 13C NMR spectroscopy in CD3CN, show that coordination of L occurs across the lanthanide series, even though complexes can only be isolated from Eu onwards. Analysis of the 31P NMR paramagnetic shifts shows that there is a break in the solution structures with a difference between the lighter lanthanides (La–Eu) and heavier metals (Tb–Lu) which implies a minor difference in structures. The isolated complexes are very poorly soluble, but in CDCl3, NMR measurements show dissociation into [Ln(NO3)3L2] and 2L occurs. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe)
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18 pages, 6557 KiB  
Article
Stannylenes and Germylenes Stabilized by Tetradentate Bis(amidine) Ligands with a Rigid Naphthalene Backbone
by Alejandra Acuña, Sonia Mallet-Ladeira, Jean-Marc Sotiropoulos, Eddy Maerten, Alan R. Cabrera, Antoine Baceiredo, Tsuyoshi Kato, René S. Rojas and David Madec
Molecules 2024, 29(2), 325; https://doi.org/10.3390/molecules29020325 - 9 Jan 2024
Cited by 2 | Viewed by 1618
Abstract
An unusual series of germylenes and stannylenes stabilized by new tetradentate bis(amidine) ligands RNC(R′)N-linker-NC(R′)NR with a rigid naphthalene backbone has been prepared by protonolysis reaction of Lappert’s metallylenes [M(HMDS)2] (M = Ge or Sn). Germylenes and stannylenes were fully characterized by [...] Read more.
An unusual series of germylenes and stannylenes stabilized by new tetradentate bis(amidine) ligands RNC(R′)N-linker-NC(R′)NR with a rigid naphthalene backbone has been prepared by protonolysis reaction of Lappert’s metallylenes [M(HMDS)2] (M = Ge or Sn). Germylenes and stannylenes were fully characterized by NMR spectroscopy and X-ray diffraction analysis. DFT calculations have been performed to clarify the structural and electronic properties associated with tetradentate bis(amidine) ligands. Stannylene L1Sn shows reactivity through oxidation, oxidative addition, and transmetalation reactions, affording the corresponding gallium and aluminum derivatives. Full article
(This article belongs to the Special Issue Inorganic Chemistry in Europe)
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