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Metal Clusters – Past, Current and Future Aspects

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

Deadline for manuscript submissions: closed (30 November 2023) | Viewed by 4311

Special Issue Editors


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Guest Editor
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
Interests: metal clusters; high temperature reactions; self-assembly; ligand exchange; crystal structure; luminescence; chemical and functional properties

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Guest Editor
Equipe Chimie du Solide et Matériaux, Université de Rennes 1, 35042 Rennes, France
Interests: supramolecular chemistry; self-assembling; nanocomposite; luminescence; hybrid material; liquid crystal; polymer
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Special Issue Information

Dear Colleagues,

This Special Issue is devoted to various aspects of the chemistry of discrete molecular transition metal clusters, whose properties and applications very often differ from more familiar mononuclear compounds. Two main classes of clusters can be distinguished. They are low-valent or organometallic clusters, and high-valent or inorganic clusters (mainly chalcogenide and halide-bridged), which are characterized by great structural diversity and a plethora of potentially useful physico-chemical properties. These features are often combined with the stability of the cluster core (in ligand exchange processes and redox reactions) and the relatively simple modification of the ligand environment. Both types of clusters are considered as model objects for heterogeneous catalysts on metal surfaces (organometallic clusters) and metal chalcogenides (chalcogenide metal clusters). In addition, molecular clusters themselves are effective catalysts and can catalyze quite a few reactions better than mononuclear catalysts. In other words, molecular clusters are an intermediate link between mononuclear complexes and heterogeneous catalysts, and also represent a bridge between molecular and solid state chemistry. Their study opens up new prospects in material science, catalysis, and fundamental chemistry.

Of particular interest are luminescent metal cluster complexes. Recent investigations of the photophysical and biological properties of such cluster complexes support the potential applicability of them in biology, medicine, sensorics and technology of new luminescent materials.

Prof. Dr. Konstantin Brylev
Dr. Yann Molard
Guest Editors

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Keywords

  • metal clusters
  • synthesis
  • structural features
  • functional properties
  • cluster-based materials, applications

Published Papers (4 papers)

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Research

16 pages, 3336 KiB  
Article
Water-Soluble Polyoxometal Clusters of Molybdenum (V) with Pyrazole and Triazole: Synthesis and Study of Cytotoxicity and Antiviral Activity
by Anna V. Konkova, Iulia V. Savina, Darya V. Evtushok, Tatiana N. Pozmogova, Maria V. Solomatina, Alina R. Nokhova, Alexander Y. Alekseev, Natalia V. Kuratieva, Ilia V. Eltsov, Vadim V. Yanshole, Aleksander M. Shestopalov, Anton A. Ivanov and Michael A. Shestopalov
Molecules 2023, 28(24), 8079; https://doi.org/10.3390/molecules28248079 - 14 Dec 2023
Cited by 1 | Viewed by 798
Abstract
Among well-studied and actively developing compounds are polyoxometalates (POMs), which show application in many fields. Extending this class of compounds, we introduce a new subclass of polyoxometal clusters (POMCs) [Mo12O28(μ-L)8]4− (L = pyrazolate (pz) or triazolate [...] Read more.
Among well-studied and actively developing compounds are polyoxometalates (POMs), which show application in many fields. Extending this class of compounds, we introduce a new subclass of polyoxometal clusters (POMCs) [Mo12O28(μ-L)8]4− (L = pyrazolate (pz) or triazolate (1,2,3-trz or 1,2,4-trz)), structurally similar to POM, but containing binuclear Mo2O4 clusters linked by bridging oxo- and organic ligands. The complexes obtained by ampoule synthesis from the binuclear cluster [Mo2O4(C2O4)2(H2O)2]2− in a melt of an organic ligand are soluble and stable in aqueous solutions. In addition to the detailed characterization in solid state and in aqueous solution, the biological properties of the compounds on normal and cancer cells were investigated, and antiviral activity against influenza A virus (subtype H5N1) was demonstrated. Full article
(This article belongs to the Special Issue Metal Clusters – Past, Current and Future Aspects)
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18 pages, 4114 KiB  
Article
From K6[Re6−xMoxS8(CN)5] Solid Solution to Individual Cluster Complexes: Separation and Investigation of [Re4Mo2S8(CN)6]n− and [Re3Mo3S8(CN)6]n− Heterometallic Clusters
by Tatiana I. Lappi, Yakov M. Gayfulin, Adèle Renaud, Carmelo Prestipino, Pierric Lemoine, Vadim V. Yanshole, Viktoria K. Muravieva, Stéphane Cordier and Nikolai G. Naumov
Molecules 2023, 28(15), 5875; https://doi.org/10.3390/molecules28155875 - 04 Aug 2023
Cited by 1 | Viewed by 657
Abstract
A series of new cluster compounds with {Re4Mo2S8} and {Re3Mo3S8} cores has been obtained and investigated. The clusters with different Re/Mo ratios were isolated as individual compounds, which made it possible [...] Read more.
A series of new cluster compounds with {Re4Mo2S8} and {Re3Mo3S8} cores has been obtained and investigated. The clusters with different Re/Mo ratios were isolated as individual compounds, which made it possible to study their spectroscopic and electrochemical properties. The geometry of the new clusters was studied using a combination of X-ray diffraction analysis, XAS and quantum chemical DFT calculations. It was shown that the properties of the new clusters, such as the number and position of electrochemical transitions, electronic structure and change in geometry with a change in charge, are similar to the properties of clusters based on the {Re4Mo2Se8} and {Re3Mo3Se8} cores described earlier. Full article
(This article belongs to the Special Issue Metal Clusters – Past, Current and Future Aspects)
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12 pages, 5798 KiB  
Article
Sea-Cucumber-like Microstructure Polyoxometalate/TiO2 Nanocomposite Electrode for High-Performance Electrochromic Energy Storage Devices
by Xiaoshu Qu, Lili Zhou, Zefeng Liu, Zeyu Wang, Jilong Wang, Xiaoyang Yu, Hua Jin and Yanyan Yang
Molecules 2023, 28(6), 2634; https://doi.org/10.3390/molecules28062634 - 14 Mar 2023
Cited by 1 | Viewed by 1281
Abstract
The key challenge in the practical application of electrochromic energy storage devices (EESDs) is the fabrication of high-performance electrode materials. Herein, we deposited K7[La(H2O)x2-P2W17O61)] (P2W17La) [...] Read more.
The key challenge in the practical application of electrochromic energy storage devices (EESDs) is the fabrication of high-performance electrode materials. Herein, we deposited K7[La(H2O)x2-P2W17O61)] (P2W17La) onto TiO2 nanowires (NW) to construct an NW–P2W17La nanocomposite using a layer-by-layer self-assembly method. In contrast to the pure P2W17La films, the nanocomposite exhibits enhanced electrochromic and electrochemical performance owing to the 3D sea-cucumber-like microstructure. An EESD using the NW–P2W17La film as the cathode exhibited outstanding electrochromic and energy storage properties, with high optical modulation (48.6% at 605 nm), high switching speeds (tcoloring = 15 s, tbleaching = 4 s), and high area capacitance (5.72 mF cm−2 at 0.15 mA cm−2). The device can reversibly switch between transparent and dark blue during the charge/discharge process, indicating that electrochromic contrast can be used as a quantitative indicator of the energy storage status. Full article
(This article belongs to the Special Issue Metal Clusters – Past, Current and Future Aspects)
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9 pages, 1467 KiB  
Communication
A Novel Photoluminescent Ag/Cu Cluster Exhibits a Chromic Photoluminescence Response towards Volatile Organic Vapors
by Wei Yang, Shengnan Hu, Yuwei Wang, Sisi Yan, Xiang-Qian Cao, Hong-Xi Li, David James Young and Zhi-Gang Ren
Molecules 2023, 28(3), 1257; https://doi.org/10.3390/molecules28031257 - 27 Jan 2023
Viewed by 1144
Abstract
A new Ag/Cu bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(EtOH)2](ClO4)4 (1, bdppthi = N,N′-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) exhibited strong phosphorescent (PL) emission at 644 nm upon excitation at 400 nm. Removal of [...] Read more.
A new Ag/Cu bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(EtOH)2](ClO4)4 (1, bdppthi = N,N′-bis(diphenylphosphanylmethyl)-tetrahydroimidazole) exhibited strong phosphorescent (PL) emission at 644 nm upon excitation at 400 nm. Removal of the coordinated EtOH molecules in 1 resulted in derivative 1a, which exhibited significant red-shifted emission at 678 nm. The structure and PL of 1 was restored on exposure to EtOH vapor. Cluster 1a also exhibited a vapor-chromic PL response towards other common organic solvent vapors including acetone, MeOH and MeCN. A PMMA film of 1a was developed as a reusable visible sensor for MeCN. Full article
(This article belongs to the Special Issue Metal Clusters – Past, Current and Future Aspects)
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