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Oligonuclear Metal Complexes with Schiff Base Ligands 2.0

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 9630

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Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Modena e Reggio Emilia, 41125 Modena, Italy
Interests: coordination chemistry; electronic modulation; structure-property correlation studies; Schiff base ligands; magnetic properties
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Special Issue Information

Dear Colleagues, 

The well-known and heterogeneous class of Schiff base ligands, named in this way after Hugo Schiff’s discoveries in the 19th century, has been developed in all fields for a very long time, and there are innumerous examples of metal complexes, ranging from mono- to oligo-nuclear and polymeric systems, and incorporating both transition metals and rare earth ions.

Nevertheless, new compounds with interesting properties and promising applications as new materials appear every day in the literature, which highlights the fact that the research with Schiff bases is still strongly active and very productive. Ranging from new synthesis to the rediscovery of known compounds, metal complexes with polydentate Schiff base ligands can be very attractive for their spectroscopic, magnetic, optical and biological properties, as well as for their reactivity and applications as efficient catalysts. 

This Special Issue of the prestigious International Journal of Molecular Sciences in the Section ‘Physical Chemistry and Chemical Physics’ aims to collect original research papers as well as focused reviews in order to showcase the undiscovered potentials of oligonuclear Schiff base metal complexes and the study of their chemico-physical features from both the experimental and the theoretical points of view. 

Prof. Dr. Luca Rigamonti 
Guest Editor

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Keywords

  • Polydentate schiff bases
  • Transition metals
  • Lanthanides
  • Oligonuclear complexes
  • Coordination compounds
  • Spectroscopic properties
  • Molecular structure
  • Supramolecular assembly
  • Physical properties
  • Theoretical calculations
  • Catalysis
  • Biological applications
  • Medicinal chemistry
  • Optical properties
  • Magnetic properties

Published Papers (5 papers)

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Research

15 pages, 1785 KiB  
Article
Substituent-Guided Cluster Nuclearity for Tetranuclear Iron(III) Compounds with Flat {Fe43-O)2} Butterfly Core
by Lorenzo Marchi, Stefano Carlino, Carlo Castellano, Francesco Demartin, Alessandra Forni, Anna M. Ferretti, Alessandro Ponti, Alessandro Pasini and Luca Rigamonti
Int. J. Mol. Sci. 2023, 24(6), 5808; https://doi.org/10.3390/ijms24065808 - 18 Mar 2023
Cited by 2 | Viewed by 1247
Abstract
The tetranuclear iron(III) compounds [Fe43-O)2(μ-LZ)4] (13) were obtained by reaction of FeCl3 with the shortened salen-type N2O2 tetradentate Schiff bases N,N’-bis(salicylidene)-o [...] Read more.
The tetranuclear iron(III) compounds [Fe43-O)2(μ-LZ)4] (13) were obtained by reaction of FeCl3 with the shortened salen-type N2O2 tetradentate Schiff bases N,N’-bis(salicylidene)-o-Z-phenylmethanediamine H2LZ (Z = NO2, Cl and OMe, respectively), where the one-carbon bridge between the two iminic nitrogen donor atoms guide preferentially to the formation of oligonuclear species, and the ortho position of the substituent Z on the central phenyl ring selectively drives towards Fe4 bis-oxido clusters. All compounds show a flat almost-symmetric butterfly-like conformation of the {Fe43-O)2} core, surrounded by the four Schiff base ligands, as depicted by both the X-ray molecular structures of 1 and 2 and the optimized geometries of all derivatives as obtained by UM06/6-311G(d) DFT calculations. The strength of the antiferromagnetic exchange coupling constants between the iron(III) ions varies among the three derivatives, despite their magnetic cores remain structurally almost unvaried, as well as the coordination of the metal ions, with a distorted octahedral environment for the two-body iron ions, Feb, and a pentacoordination with trigonal bipyramidal geometry for the two-wing iron ions, Few. The different magnetic behavior within the series of examined compounds may be ascribed to the influence of the electronic features of Z on the electron density distribution (EDD) of the central {Fe43-O)2} core, substantiated by a Quantum Theory of Atoms In Molecules (QTAIM) topological analysis of the EDD, as obtained by UM06 calculations 13. Full article
(This article belongs to the Special Issue Oligonuclear Metal Complexes with Schiff Base Ligands 2.0)
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24 pages, 12402 KiB  
Article
New Dinuclear Macrocyclic Copper(II) Complexes as Potentially Fluorescent and Magnetic Materials
by Magdalena Barwiolek, Dominika Jankowska, Anna Kaczmarek-Kędziera, Iwona Lakomska, Jedrzej Kobylarczyk, Robert Podgajny, Paweł Popielarski, Joanna Masternak, Maciej Witwicki and Tadeusz M. Muzioł
Int. J. Mol. Sci. 2023, 24(3), 3017; https://doi.org/10.3390/ijms24033017 - 03 Feb 2023
Cited by 3 | Viewed by 2534
Abstract
Two dinuclear copper(II) complexes with macrocyclic Schiff bases K1 and K2 were prepared by the template reaction of (R)-(+)-1,1′-binaphthalene-2,2′-diamine and 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde K1, or 4-tert-butyl-2,6-diformylphenol K2 with copper(II) chloride dihydrate. The compounds were characterized by spectroscopic methods. X-ray crystal [...] Read more.
Two dinuclear copper(II) complexes with macrocyclic Schiff bases K1 and K2 were prepared by the template reaction of (R)-(+)-1,1′-binaphthalene-2,2′-diamine and 2-hydroxy-5-methyl-1,3-benzenedicarboxaldehyde K1, or 4-tert-butyl-2,6-diformylphenol K2 with copper(II) chloride dihydrate. The compounds were characterized by spectroscopic methods. X-ray crystal structure determination and DFT calculations confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of K2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The magnetic study revealed very strong antiferromagnetic CuII-CuII exchange interactions, which were supported by magneto-structural correlation and DFT calculations conducted within a broken symmetry (BS) framework. Complexes K1 and K2 exhibited luminescent properties that may be of great importance in the search for new OLEDs. Both K1 and K2 complexes showed emissions in the range of 392–424 nm in solutions at various polarities. Thin materials of the studied compounds were deposited on Si(111) by the spin-coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), and fluorescence spectroscopy. The thermally deposited K1 and K2 materials showed high fluorescence intensity in the range of 318–531 nm for K1/Si and 326–472 nm for the K2/Si material, indicating that they could be used in optical devices. Full article
(This article belongs to the Special Issue Oligonuclear Metal Complexes with Schiff Base Ligands 2.0)
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19 pages, 3622 KiB  
Article
Investigations on the Influence of the Axial Ligand in [Salophene]iron(III) Complexes on Biological Activity and Redox Behavior
by Hubert Descher, Sophie Luise Strich, Martin Hermann, Peter Enoh, Brigitte Kircher and Ronald Gust
Int. J. Mol. Sci. 2023, 24(3), 2173; https://doi.org/10.3390/ijms24032173 - 21 Jan 2023
Cited by 1 | Viewed by 2088
Abstract
The [N,N′-disalicylidene-1,2-phenylenediamine]iron(III) ([salophene]iron(III)) derivatives 14 with anionic axial ligands (A = Cl, NO3, SCN, CH3COO) and complexes 5 and 6 with neutral ligands (A = imidazole, 1-methylimidazole) as [...] Read more.
The [N,N′-disalicylidene-1,2-phenylenediamine]iron(III) ([salophene]iron(III)) derivatives 14 with anionic axial ligands (A = Cl, NO3, SCN, CH3COO) and complexes 5 and 6 with neutral ligands (A = imidazole, 1-methylimidazole) as well as the μ-oxo dimer 7 inhibited proliferation, reduced metabolic activity, and increased mitochondrial reactive oxygen species. Ferroptosis as part of the mode of action was identified by inhibitor experiments, together with induction of lipid peroxidation and diminished mitochondrial membrane potential. No differences in activity were observed for all compounds except 4, which was slightly less active. Electrochemical analyses revealed for all compounds a fast attachment of the solvent dimethyl sulfoxide and a release of the axial ligand A. In contrast, in dichloromethane and acetonitrile, ligand exchange did not take place, as analyzed by measurements of the standard potential for the iron(III/II) redox reaction. Full article
(This article belongs to the Special Issue Oligonuclear Metal Complexes with Schiff Base Ligands 2.0)
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19 pages, 3937 KiB  
Article
Ligand-Modulated Nuclearity and Geometry in Nickel(II) Hydrazone Complexes: From Mononuclear Complexes to Acetato- and/or Phenoxido-Bridged Clusters
by Višnja Vrdoljak, Tomica Hrenar, Mirta Rubčić, Gordana Pavlović, Tomislav Friganović and Marina Cindrić
Int. J. Mol. Sci. 2023, 24(3), 1909; https://doi.org/10.3390/ijms24031909 - 18 Jan 2023
Cited by 3 | Viewed by 1279
Abstract
The propensity of 4-hydroxybenzhydrazone-related ligands derived from 3-methoxysalicylaldehyde (H2L3OMe), 4-methoxysalicylaldehyde (H2L4OMe), and salicylaldehyde (H2LH) to act as chelating and/or bridging ligands in Ni(II) complexes was investigated. Three clusters of different nuclearities, [...] Read more.
The propensity of 4-hydroxybenzhydrazone-related ligands derived from 3-methoxysalicylaldehyde (H2L3OMe), 4-methoxysalicylaldehyde (H2L4OMe), and salicylaldehyde (H2LH) to act as chelating and/or bridging ligands in Ni(II) complexes was investigated. Three clusters of different nuclearities, [Ni3(L3OMe)2(OAc)2(MeOH)2]∙2MeOH∙MeCN (1∙2MeOH∙MeCN), [Ni2(HL4OMe)(L4OMe)(OAc)(MeOH)2]∙4.7MeOH (2∙4.7MeOH), and [Ni4(HLH)2(LH)2(OAc)2]∙4MeOH·0.63H2O·0.5MeCN·HOAc (3∙4MeOH·0.63H2O·0.5MeCN·HOAc), were prepared from Ni(OAc)2∙4H2O and the corresponding ligand in the presence of Et3N. The hydrazones in these acetato- and phenoxido-bridged clusters acted as singly or doubly deprotonated ligands. When pyridine was used, mononuclear complexes with the square-planar geometry seemed to be favoured, as found for complexes [Ni(L3OMe)(py)] (4), [Ni(L4Ome)(py)] (5) and [Ni(LH)(py)] (6). Ligand substituent effects and the stability of square-planar complexes were investigated and quantified by extensive quantum chemical analysis. Obtained results showed that standard Gibbs energies of binding were lower for square-planar than for octahedral complexes. Starting from [MoO2(L)(EtOH)] complexes as precursors and applying the metal-exchange procedure, the mononuclear complexes [Ni(HL3OMe)2]∙MeOH (7∙MeOH) and [Ni(HLH)]∙2MeOH (9∙2MeOH) and hybrid organic–inorganic compound [Ni2(HL4OMe)2(CH3OH)4][Mo4O10(OCH3)6] (10) were achieved. The octahedral complexes [Ni(HL)2] (79) can also be obtained by the direct synthesis from Ni(Oac)2∙4H2O and the appropriate ligand under specific reaction conditions. Crystal and molecular structures of 1∙2MeOH∙MeCN, 2∙4.7MeOH, 3∙4MeOH∙0.63H2O∙0.5MeCN∙HOAc, 4, 5, 9∙2MeOH, and 10 were determined by the single-crystal X-ray diffraction method. Full article
(This article belongs to the Special Issue Oligonuclear Metal Complexes with Schiff Base Ligands 2.0)
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7 pages, 1697 KiB  
Communication
Oxygen Binding by Co(II) Complexes with Oxime-Containing Schiff Bases in Solution
by Marek Pająk, Magdalena Woźniczka, Marta E. Lichawska, Bartłomiej Czerwiński, Jakub Włodarczyk and Jakub Fichna
Int. J. Mol. Sci. 2022, 23(10), 5492; https://doi.org/10.3390/ijms23105492 - 14 May 2022
Cited by 1 | Viewed by 1698
Abstract
The present work describes the complexation properties of two oxime-containing Schiff bases (used as ligands), viz. 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) and 2-hydroxyimino-N′-[(pyridine-2-yl)methylidene]propanohydrazone (Hpoa), with Co(II) ions in DMSO/water solution. Volumetric (oxygenation) studies were carried out to determine the uptake of molecular oxygen O2 in [...] Read more.
The present work describes the complexation properties of two oxime-containing Schiff bases (used as ligands), viz. 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) and 2-hydroxyimino-N′-[(pyridine-2-yl)methylidene]propanohydrazone (Hpoa), with Co(II) ions in DMSO/water solution. Volumetric (oxygenation) studies were carried out to determine the uptake of molecular oxygen O2 in the formation of the complexes Co(II)-Hpop and Co(II)-Hpoa. The acquired data can be useful in the development of oxygen bioinorganic complexes of metal ions with Schiff base ligands in solution. Their properties allow them to be used as synthetic oxygen transporters. Moreover, the binding of dioxygen could play an important role in the research of catalytic activity by such systems. Full article
(This article belongs to the Special Issue Oligonuclear Metal Complexes with Schiff Base Ligands 2.0)
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