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Frontiers in Metal Complexes
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Frontiers in Metal Complexes

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

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 10020

Special Issue Editor

Prof. Dr. Andrei V. Churakov

E-Mail Website
Guest Editor
N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
Interests: crystal engineering; supramolecular chemistry; crystal packing; weak secondary interactions; H-bonded networks; hydrogen peroxide; peroxosolvates; [2+2]photocycloaddition
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

In recent decades, metal complexes have become of great importance to modern human life. Without them, it is impossible to imagine the modern chemical, microelectronics, and pharmaceutical industries. It is clear that in the future the role of complex compounds will only increase, especially in key areas of development such as energy-saving technologies, medicine, green chemistry, and environmental protection.

We are pleased to invite you to participate in a Special Issue titled “Frontiers in Metal Complexes”. The main attention will be paid to complexes with an unusual molecular and crystal structure, which could lead to the emergence of promising chemical and physical properties for the preparation of new effective materials, catalysts, and drugs.

Prof. Dr. Andrei Churakov
Guest Editor

Manuscript Submission Information

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Keywords

  • unusual coordination environment
  • unusual oxidation states
  • inner-sphere reactions
  • C-H activation
  • stereoselective catalysis
  • photoactive complexes
  • anticancer activity of metal complexes

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Published Papers (4 papers)

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Research

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9 pages, 901 KiB  
Article
First Example of Cage P4N4-Macrocycle Copper Complexes with Intracavity Location of Unusual Cu2I Fragments
by Anna S. Balueva, Yulia A. Nikolaeva, Elvira I. Musina, Igor A. Litvinov and Andrey A. Karasik
Molecules 2023, 28(2), 680; https://doi.org/10.3390/molecules28020680 - 9 Jan 2023
Cited by 1 | Viewed by 1267
Abstract
In this study, 28-membered macrocyclic 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane were synthesized by condensation of pyridinephosphine, paraformaldehyde, and primary diamines (bis(4-aminophenyl)methane or -sulfide. The first representatives of binuclear copper(I) complexes of P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into a macrocyclic core and intracavity location of unusual, [...] Read more.
In this study, 28-membered macrocyclic 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane were synthesized by condensation of pyridinephosphine, paraformaldehyde, and primary diamines (bis(4-aminophenyl)methane or -sulfide. The first representatives of binuclear copper(I) complexes of P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane rings incorporated into a macrocyclic core and intracavity location of unusual, developed angle Cu2I moiety were obtained. The structure of one complex was established by X-ray diffraction analysis. The complexation led to a slight distortion of the cyclophane conformations. Full article
(This article belongs to the Special Issue Frontiers in Metal Complexes)
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24 pages, 7978 KiB  
Article
Aerogel-Based Single-Ion Magnets: A Case Study of a Cobalt(II) Complex Immobilized in Silica
by Sergey Yu. Kottsov, Maxim A. Shmelev, Alexander E. Baranchikov, Mikhail A. Kiskin, Alim U. Sharipov, Nikolay N. Efimov, Irina K. Rubtsova, Stanislav A. Nikolaevskii, Gennady P. Kopitsa, Tamara V. Khamova, Ilya V. Roslyakov, Igor L. Eremenko and Vladimir K. Ivanov
Molecules 2023, 28(1), 418; https://doi.org/10.3390/molecules28010418 - 3 Jan 2023
Cited by 6 | Viewed by 2747
Abstract
The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on [...] Read more.
The chemical immobilization of cobalt(II) ions in a silica aerogel matrix enabled the synthesis of the first representative example of aerogel-based single-ion magnets. For the synthesis of the lyogels, methyl-trimethoxysilane and N-3-(trimethoxysilyl)propyl ethylenediamine were co-hydrolyzed, then the ethylenediamine groups that were immobilized on the silica matrix enabled the subsequent binding of cobalt(II) ions. Lyogels with various amounts of ethylenediamine moieties (0.1–15 mol %) were soaked in isopropanol solutions of cobalt(II) nitrate and further supercritically dried in carbon dioxide to obtain aerogels with a specific surface area of 210–596 m2·g−1, an apparent density of 0.403–0.740 cm3·g−1 and a porosity of 60–78%. The actual cobalt content in the aerogels was 0.01–1.50 mmol per 1 g of SiO2, which could easily be tuned by the concentration of ethylenediamine moieties in the silica matrix. The introduction of cobalt(II) ions into the ethylenediamine-modified silica aerogel promoted the stability of the diamine moieties at the supercritical drying stage. The molecular prototype of the immobilized cobalt(II) complex, bearing one ethylenediamine ligand [Co(en)(MeCN)(NO3)2], was synthesized and structurally characterized. Using magnetometry in the DC mode, it was shown that cobalt(II)-modified silica aerogels exhibited slow magnetic relaxation in a nonzero field. A decrease in cobalt(II) concentration in aerogels from 1.5 mmol to 0.14 mmol per 1 g of SiO2 resulted in a weakening of inter-ion interactions; the magnetization reversal energy barrier likewise increased from 4 to 18 K. Full article
(This article belongs to the Special Issue Frontiers in Metal Complexes)
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16 pages, 3849 KiB  
Article
A Panchromatic Cyclometalated Iridium Dye Based on 2-Thienyl-Perimidine
by Paulina Kalle, Marina A. Kiseleva, Sergei V. Tatarin, Daniil E. Smirnov, Alexander Y. Zakharov, Viktor V. Emets, Andrei V. Churakov and Stanislav I. Bezzubov
Molecules 2022, 27(10), 3201; https://doi.org/10.3390/molecules27103201 - 17 May 2022
Cited by 10 | Viewed by 2322
Abstract
Though 2-arylperimidines have never been used in iridium(III) chemistry, the present study on structural, electronic and optical properties of N-unsubstituted and N-methylated 2-(2-thienyl)perimidines, supported by DFT/TDDFT calculations, has shown that these ligands are promising candidates for construction of light-harvesting iridium(III) complexes. [...] Read more.
Though 2-arylperimidines have never been used in iridium(III) chemistry, the present study on structural, electronic and optical properties of N-unsubstituted and N-methylated 2-(2-thienyl)perimidines, supported by DFT/TDDFT calculations, has shown that these ligands are promising candidates for construction of light-harvesting iridium(III) complexes. In contrast to N-H perimidine, the N-methylated ligand gave the expected cyclometalated μ-chloro-bridged iridium(III) dimer which was readily converted to a cationic heteroleptic complex with 4,4′-dicarboxy-2,2′-bipyridine. The resulting iridium(III) dye exhibited panchromatic absorption up to 1000 nm and was tested in a dye-sensitized solar cell. Full article
(This article belongs to the Special Issue Frontiers in Metal Complexes)
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Review

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62 pages, 20590 KiB  
Review
Transition Metal–(μ-Cl)–Aluminum Bonding in α-Olefin and Diene Chemistry
by Ilya E. Nifant’ev, Ildar I. Salakhov and Pavel V. Ivchenko
Molecules 2022, 27(21), 7164; https://doi.org/10.3390/molecules27217164 - 23 Oct 2022
Cited by 5 | Viewed by 3025
Abstract
Olefin and diene transformations, catalyzed by organoaluminum-activated metal complexes, are widely used in synthetic organic chemistry and form the basis of major petrochemical processes. However, the role of M–(μ-Cl)–Al bonding, being proven for certain >C=C< functionalization reactions, remains unclear and debated for essentially [...] Read more.
Olefin and diene transformations, catalyzed by organoaluminum-activated metal complexes, are widely used in synthetic organic chemistry and form the basis of major petrochemical processes. However, the role of M–(μ-Cl)–Al bonding, being proven for certain >C=C< functionalization reactions, remains unclear and debated for essentially more important industrial processes such as oligomerization and polymerization of α-olefins and conjugated dienes. Numerous publications indirectly point at the significance of M–(μ-Cl)–Al bonding in Ziegler–Natta and related transformations, but only a few studies contain experimental or at least theoretical evidence of the involvement of M–(μ-Cl)–Al species into catalytic cycles. In the present review, we have compiled data on the formation of M–(μ-Cl)–Al complexes (M = Ti, Zr, V, Cr, Ni), their molecular structure, and reactivity towards olefins and dienes. The possible role of similar complexes in the functionalization, oligomerization and polymerization of α-olefins and dienes is discussed in the present review through the prism of the further development of Ziegler–Natta processes and beyond. Full article
(This article belongs to the Special Issue Frontiers in Metal Complexes)
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