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The Design, Synthesis and Study of Metal Complexes

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 (20 November 2023) | Viewed by 12041

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Guest Editor
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Acad. Lavrentyev Ave. 3, Novosibirsk 630090, Russia
Interests: the synthesis and study of the magnetic and biological activity of metal coordination compounds with nitrogen-containing heterocyclic ligands

Special Issue Information

Dear colleagues,

The International Journal of Molecular Sciences is planning to launch a new Special Issue, entitled "The Design, Synthesis and Study of Metal Complexes". The issue will focus on the development of modern physicochemical methods for the synthesis of new coordination compounds of metals with ligands of different classes, the identification of the obtained compounds and the study of their structure and properties. Comprehensive fundamental and applied research can establish more effective practical application of coordination compounds in various fields, including science, medicine, industry and agriculture. Due to the diversity of transition metals, the variability in their oxidation states, and the almost limitless variety of ligands (both organic and inorganic), the chemistry of coordination compounds provides researchers with ample opportunities for directed design to obtain compounds with the desired properties. We invite authors to submit their work to this Special Issue, which we hope will serve as a significant contribution to the development of coordination compound chemistry.

Prof. Dr. Lyudmila G. Lavrenova
Guest Editor

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Keywords

  • coordination compounds
  • metals
  • ligands
  • development of synthesis methods
  • study of the properties of complexes via physicochemical methods
  • practical application of complexes

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Published Papers (7 papers)

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Research

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25 pages, 9698 KiB  
Article
Development of Novel Nano-Sized Imine Complexes Using Coriandrum sativum Extract: Structural Elucidation, Non-Isothermal Kinetic Study, Theoretical Investigation and Pharmaceutical Applications
by Shimaa Hosny, Randa F. Abd El-Baki, Zeinab H. Abd El-Wahab, Gamal A. Gouda, Mohammed S. Saddik, Ateyatallah Aljuhani and Ahmed M. Abu-Dief
Int. J. Mol. Sci. 2023, 24(18), 14259; https://doi.org/10.3390/ijms241814259 - 19 Sep 2023
Cited by 19 | Viewed by 1422
Abstract
A new Schiff base (H2L) generated from sulfamethazine (SMT), as well as its novel micro- and nanocomplexes with Ni(II) and Cd(II) metal ions, have been synthesized. The proposed structures of all isolated solid compounds were identified with physicochemical, spectral, and thermal [...] Read more.
A new Schiff base (H2L) generated from sulfamethazine (SMT), as well as its novel micro- and nanocomplexes with Ni(II) and Cd(II) metal ions, have been synthesized. The proposed structures of all isolated solid compounds were identified with physicochemical, spectral, and thermal techniques. Molar conductance studies confirmed that the metal complexes are not electrolytic. The molecular geometry located at the central metal ion was found to be square planar for the NiL2 and tetrahedral for the CdL2 complexes. The kinetic and thermal parameters were obtained using the Coats and Redfern approach. Coriandrum sativum (CS) in ethanol was used to create the eco-friendly Ni and Cd nanocomplexes. The size of the obtained nanoparticles was examined using PXRD and TEM, and found to be in the sub-nano range (3.07–4.61 nm). Furthermore, the TEM micrograph demonstrated a uniform and homogeneous surface morphology. The chemistry of the prepared nanocomplexes was studied using TGA and TEM techniques. The effect of temperature on the prepared nanocomplexes’ size revealed a decrease in size by heating. Furthermore, the nanocomplexes’ antimicrobial and anticancer properties were evaluated. The outcomes demonstrated that the nanocomplexes exhibited better antimicrobial properties. Moreover, the antitumor results showed that after heating, the Ni nanocomplex exhibited a substantial antitumor activity (IC50 = 1.280 g/mL), which was higher than the activity of cis-platin (IC50 = 1.714 g/mL). Finally, molecular-docking studies were performed to understand the evaluated compounds’ ability to bind to methionine adenosyl-transferases (PDB ID: 5A19) in liver cancer and COVID-19 main protease (PDB ID: 6lu7) cell-proteins. The findings reveal that [NiL2]·1.5H2O2 has a higher binding energy of −37.5 kcal/mol with (PDB ID: 5A19) cell protein. Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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21 pages, 5866 KiB  
Article
Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties
by Iulia V. Savina, Anton A. Ivanov, Ilia V. Eltsov, Vadim V. Yanshole, Natalia V. Kuratieva, Andrey Y. Komarovskikh, Mikhail M. Syrokvashin and Michael A. Shestopalov
Int. J. Mol. Sci. 2023, 24(18), 13879; https://doi.org/10.3390/ijms241813879 - 9 Sep 2023
Cited by 1 | Viewed by 1103
Abstract
The chemistry of transition metal clusters has been intensively developed in the last decades, leading to the preparation of a number of compounds with promising and practically useful properties. In this context, the present work demonstrates the preparation and study of the reactivity, [...] Read more.
The chemistry of transition metal clusters has been intensively developed in the last decades, leading to the preparation of a number of compounds with promising and practically useful properties. In this context, the present work demonstrates the preparation and study of the reactivity, i.e., the possibility of varying the ligand environment, of new square pyramidal molybdenum chalcogenide clusters [{Mo53-S)i44-S)i(μ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). The one-step synthesis starting from the octahedral Mo6Br12 cluster as well as the substitution of the apical pyrazole ligand or the selective bromination of the inner pyrazolate ligands were demonstrated. All the obtained compounds were characterized in detail using a series of physicochemical methods both in solid state (X-ray diffraction analysis, etc.) and in solution (nuclear magnetic resonance spectroscopy, mass spectrometry, etc.). In this work, redox properties and absorption in the ultraviolet-visible and near-infrared region of the obtained compounds were studied. Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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19 pages, 7588 KiB  
Article
Synthesis, Structure, and Magnetic and Biological Properties of Copper(II) Complexes with 1,3,4-Thiadiazole Derivatives
by Lyudmila G. Lavrenova, Taisiya S. Sukhikh, Lyudmila A. Glinskaya, Svetlana V. Trubina, Valentina V. Zvereva, Alexander N. Lavrov, Lyubov S. Klyushova and Alexander V. Artem’ev
Int. J. Mol. Sci. 2023, 24(16), 13024; https://doi.org/10.3390/ijms241613024 - 21 Aug 2023
Cited by 4 | Viewed by 1731
Abstract
New coordination compounds of copper(II) with 2,5-bis(ethylthio)-1,3,4-thiadiazole (L1) and 2,5-bis(pyridylmethylthio)-1,3,4-thiadiazole (L2) with compositions Cu(L1)2Br2, Cu(L1)(C2N3)2, Cu(L2)Cl2, and Cu(L2)Br2 [...] Read more.
New coordination compounds of copper(II) with 2,5-bis(ethylthio)-1,3,4-thiadiazole (L1) and 2,5-bis(pyridylmethylthio)-1,3,4-thiadiazole (L2) with compositions Cu(L1)2Br2, Cu(L1)(C2N3)2, Cu(L2)Cl2, and Cu(L2)Br2 were prepared. The complexes were identified and studied by CHN analysis, infrared (IR) spectroscopy, powder X-Ray diffraction (XRD), and static magnetic susceptibility. The crystal structures of Cu(II) complexes with L1 were determined. The structures of the coordination core of complexes Cu(L2)Cl2 and Cu(L2)Br2 were determined by Extended X-ray absorption fine structure (EXAFS) spectroscopy. Magnetization measurements have revealed various magnetic states in the studied complexes, ranging from an almost ideal paramagnet in Cu(L1)2Br2 to alternating-exchange antiferromagnetic chains in Cu(L1)(C2N3)2, where double dicyanamide bridges provide an unusually strong exchange interaction (J1/kB ≈ −23.5 K; J2/kB ≈ −20.2 K) between Cu(II) ions. The cytotoxic activity of copper(II) complexes with L2 was estimated on the human cell lines of breast adenocarcinoma (MCF-7) and hepatocellular carcinoma (HepG2). Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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19 pages, 5104 KiB  
Article
Coordination Compound (2,3,5-Triphenyltetrazolium)2[CuBr4] as Catalyst for the Curing Process of Epoxy Vinyl Ester Binders
by Alexander E. Protsenko, Alexandra N. Protsenko, Olga G. Shakirova and Daria D. Zhelevskaya
Int. J. Mol. Sci. 2023, 24(14), 11808; https://doi.org/10.3390/ijms241411808 - 22 Jul 2023
Cited by 3 | Viewed by 1214
Abstract
This article presents a study on the synthesis and catalytic properties of copper complex (TPhTz)2[CuBr4] (here TPhTz is 2,3,5-triphenyltetrazolium). The obtained complex was characterized by various spectroscopic methods. The catalytic properties of the complex were evaluated in the curing [...] Read more.
This article presents a study on the synthesis and catalytic properties of copper complex (TPhTz)2[CuBr4] (here TPhTz is 2,3,5-triphenyltetrazolium). The obtained complex was characterized by various spectroscopic methods. The catalytic properties of the complex were evaluated in the curing of an epoxy vinyl ester system and their effectiveness was compared with that of cobalt octoate (its synonyms are known as Co(Oct)2, cobalt(II) 2-ethylhexanoate, cobalt isocaprylate, etc.). The catalyst was added at an amount of 2 w.%. The results showed that a 8 w.% solution of the complex provides catalytic properties with an activation energy of 54.7 kJ/mol, which is 25.2 kJ/mol higher than a standard curing system with Co(Oct)2. Thus, the solution of (TPhTz)2[CuBr4] in THF/DMSO accelerates the initiator decay process at room temperature, but for a longer time. The authors suggest that the curing mechanism may be accelerated by the appearance of (TPhTz)2[CuIBr3] and free bromine in the system. A strength test of fiberglass-reinforced plastic revealed that the addition of this complex did not lead to a decrease in flexural strength and hardness. Thus, use of the complex allowed for the production of polymer composite products using vacuum-assisted resin transfer molding where an extended injection time was needed. Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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18 pages, 4465 KiB  
Article
Crystal Design, Antitumor Activity and Molecular Docking of Novel Palladium(II) and Gold(III) Complexes with a Thiosemicarbazone Ligand
by Carolane M. Almeida, Érica C. M. Nascimento, João B. L. Martins, Tales H. A. da Mota, Diêgo M. de Oliveira and Claudia C. Gatto
Int. J. Mol. Sci. 2023, 24(14), 11442; https://doi.org/10.3390/ijms241411442 - 14 Jul 2023
Cited by 1 | Viewed by 1525
Abstract
The current research describes the synthesis and characterization of 2-acetylpyridine N(4)-cyclohexyl-thiosemicarbazone ligand (HL) and their two metal complexes, [Au(L)Cl][AuCl2] (1) and [Pd(L)Cl]·DMF (2). The molecular structures of the compounds were determined by physicochemical and spectroscopic methods. Single crystal X-ray diffraction [...] Read more.
The current research describes the synthesis and characterization of 2-acetylpyridine N(4)-cyclohexyl-thiosemicarbazone ligand (HL) and their two metal complexes, [Au(L)Cl][AuCl2] (1) and [Pd(L)Cl]·DMF (2). The molecular structures of the compounds were determined by physicochemical and spectroscopic methods. Single crystal X-ray diffraction was employed in the structural elucidation of the new complexes. The complexes showed a square planar geometry to the metal center Au(III) and Pd(II), coordinated with a thiosemicarbazone molecule by the NNS-donor system and a chloride ion. Complex (1) also shows the [AuCl2] counter-ion in the asymmetric unit, and complex (2) has one DMF solvent molecule. These molecules play a key role in the formation of supramolecular structures due to different interactions. Noncovalent interactions were investigated through the 3D Hirshfeld surface by the dnorm function and the 2D fingerprint plots. The biological activity of the compounds was evaluated in vitro against the human glioma U251 cells. The cytotoxicity results revealed great antitumor activity in complex (1) compared with complex (2) and the free ligand. Molecular docking simulations were used to predict interactions and properties with selected proteins and DNA of the synthesized compounds. Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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16 pages, 3119 KiB  
Article
Spin Crossover and Thermochromism in Iron(II) Complexes with 2,6-Bis(1H-imidazol-2-yl)-4-methoxypyridine
by Olga G. Shakirova, Irina A. Os’kina, Evgeniy V. Korotaev, Sergey A. Petrov, Natalia V. Kuratieva, Alexsei Ya. Tikhonov and Lyudmila G. Lavrenova
Int. J. Mol. Sci. 2023, 24(12), 9853; https://doi.org/10.3390/ijms24129853 - 7 Jun 2023
Viewed by 1542
Abstract
New iron(II) complexes with 2,6-bis(1H-imidazol-2-yl)-4-methoxypyridine (L) of the composition [FeL2]An∙mH2O (A = SO42−, n = 1, m = 2 (I); A = ReO4, n = [...] Read more.
New iron(II) complexes with 2,6-bis(1H-imidazol-2-yl)-4-methoxypyridine (L) of the composition [FeL2]An∙mH2O (A = SO42−, n = 1, m = 2 (I); A = ReO4, n = 2, m = 1 (II); A = Br, n = 2, m = 2 (III)) have been synthesized and investigated. To determine the coordination ability of the ligand, a single crystal of a copper(II) complex of the composition [CuLCl2] (IV) was obtained and studied by X-ray technique. Compounds IIII were studied using methods of X-ray phase analysis, electron (diffuse reflection spectra), infrared and Mössbauer spectroscopy, static magnetic susceptibility. The study of the µeff(T) dependence showed that the 1A15T2 spin crossover manifests itself in the compounds. The spin crossover is accompanied by thermochromism: there is a distinct color change orange ↔ red-violet. Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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Review

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34 pages, 10822 KiB  
Review
An Overview of the Potential Medicinal and Pharmaceutical Properties of Ru(II)/(III) Complexes
by Anna Skoczynska, Andrzej Lewinski, Mateusz Pokora, Piotr Paneth and Elzbieta Budzisz
Int. J. Mol. Sci. 2023, 24(11), 9512; https://doi.org/10.3390/ijms24119512 - 30 May 2023
Cited by 8 | Viewed by 2544
Abstract
This review examines the existing knowledge about Ru(II)/(III) ion complexes with a potential application in medicine or pharmacy, which may offer greater potential in cancer chemotherapy than Pt(II) complexes, which are known to cause many side effects. Hence, much attention has been paid [...] Read more.
This review examines the existing knowledge about Ru(II)/(III) ion complexes with a potential application in medicine or pharmacy, which may offer greater potential in cancer chemotherapy than Pt(II) complexes, which are known to cause many side effects. Hence, much attention has been paid to research on cancer cell lines and clinical trials have been undertaken on ruthenium complexes. In addition to their antitumor activity, ruthenium complexes are under evaluation for other diseases, such as type 2 diabetes, Alzheimer’s disease and HIV. Attempts are also being made to evaluate ruthenium complexes as potential photosensitizers with polypyridine ligands for use in cancer chemotherapy. The review also briefly examines theoretical approaches to studying the interactions of Ru(II)/Ru(III) complexes with biological receptors, which can facilitate the rational design of ruthenium-based drugs. Full article
(This article belongs to the Special Issue The Design, Synthesis and Study of Metal Complexes)
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