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Inorganic Metal-to-Ligand Clusters
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Inorganic Metal-to-Ligand Clusters

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced Composites".

Deadline for manuscript submissions: closed (20 June 2022) | Viewed by 2959

Special Issue Editors

Dr. Beñat Artetxe

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Guest Editor
Department of Inorganic Chemistry, Universidad del Pais Vasco UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain
Interests: polyoxometalates; coordination chemistry; X-ray diffraction; crystal structures; photoluminescence; solution studies
Special Issues, Collections and Topics in MDPI journals
Dr. Santiago Reinoso

E-Mail Website
Guest Editor
Departamento de Ciencias & Institute for Advanced Materials and Mathemathics (InaMat2), Universidad Pública de Navarra (UPNA), Pamplona, Spain
Interests: polyoxometalates; coordination chemistry of transition metals and rare earths; synthetic inorganic chemistry; single-crystal X-ray diffraction
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Metal-to-ligand clusters represent one of the most intriguing areas of inorganic chemistry, because they encompass polynuclear species of a very diverse nature, such as polyoxometalates, metal–organic polyhedra, and metal-chalcogenide/halide clusters. Their rich solution equilibria, together with a remarkable structural variety that allows for systematic compositional variations, have resulted in molecular entities with a wide range of properties (e.g., acidity, outstanding redox behavior, magnetism, catalytic, and/or biological activity) arising from the combination of both inorganic metal cations and non-metallic ligands. In some specific cases, the possibility of generating vacant metallic sites in a controlled way allows for their use as ligands towards additional electrophilic moieties or organic functions (e.g., transition-metal cations, rare earths, and p-block organoderivatives), thus paving the way for providing the clusters with tailored additional properties.

This Special Issue aims to emphasize the latest advances in the chemistry of such inorganic clusters by covering topics from fundamental aspects (synthesis, reactivity, spectroscopy, structure, and solution studies) to functional materials that incorporate these molecular units (organic polymers, functional surfaces, inorganic matrixes, and nanoparticles), as well as their potential applications in fields like catalysis, photo- and electrochemistry, electronics, optics, bio-medicine, energy storage, sorption, and environmental remediation.

Dr. Beñat Artetxe
Dr. Santiago Reinoso
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • polyoxometalates
  • metal-halide/chalcogenide clusters
  • coordination chemistry
  • post-functionalization
  • solution studies
  • crystallochemistry
  • functional materials
  • catalysis and magnetism
  • optics and electronics
  • biological applications

Published Papers (2 papers)

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Research

9 pages, 3597 KiB  
Article
Reversible First-Order Single Crystal to Single Crystal Thermal Phase Transition in [(CH3)3CNH3]4[V4O12]
by Pablo Vitoria, Ana San José Wéry, Leire San Felices, Laura Bravo-García, Estibaliz Ruiz-Bilbao, José Manuel Laza, José Luis Vilas and Juan M. Gutiérrez-Zorrilla
Materials 2022, 15(16), 5663; https://doi.org/10.3390/ma15165663 - 17 Aug 2022
Cited by 1 | Viewed by 893
Abstract
The well-known compound tetrakis(tert-butylammonium)-cyclo-tetrametavanadate (V), [(CH3)3CNH3]4[V4O12] (1h_RT), which crystallizes in the tetragonal I4/m space group, undergoes an irreversible solid state transformation upon heating, constituting one of the few examples in which [...] Read more.
The well-known compound tetrakis(tert-butylammonium)-cyclo-tetrametavanadate (V), [(CH3)3CNH3]4[V4O12] (1h_RT), which crystallizes in the tetragonal I4/m space group, undergoes an irreversible solid state transformation upon heating, constituting one of the few examples in which the initial and the final stages are structurally characterized by sc-XRD. Now, we observed the ability of the same compound to undergo an additional single-crystal-to-single-crystal (SCSC) transformation upon thermal stimuli, but this time at low temperatures (153 K). Compound 1h_RT contains a discrete unprotonated [V4O12]4− tetrahedral anion in which V and O bridging atoms are coplanar. In both phases, these tetrameric anions are linked through tert-butylammonium cations in an extensive network of hydrogen bonds, but at low temperatures, this phase loses its characteristic O-V-O coplanarity, with the resulting rearrangement of the crystal packing and hydrogen-bond network which provide its reversibility at low temperatures. Again, the initial and final stages have been characterized structurally by sc-XRD. Full article
(This article belongs to the Special Issue Inorganic Metal-to-Ligand Clusters)
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12 pages, 31960 KiB  
Article
Polyoxomolybdate Layered Crystals Constructed from a Heterocyclic Surfactant: Syntheses, Pseudopolymorphism and Introduction of Metal Cations
by Jun Kobayashi, Keisuke Shimura, Keisuke Mikurube, Saki Otobe, Takashi Matsumoto, Eri Ishikawa, Haruo Naruke and Takeru Ito
Materials 2022, 15(7), 2429; https://doi.org/10.3390/ma15072429 - 25 Mar 2022
Viewed by 1502
Abstract
Crystals with layered structures are crucial for the construction of functional materials exhibiting intercalation, ionic conductivity, or emission properties. Polyoxometalate crystals hybridized with surfactant cations have distinct layered packings due to the surfactants which can form lamellar structures. Introducing metal cations into such [...] Read more.
Crystals with layered structures are crucial for the construction of functional materials exhibiting intercalation, ionic conductivity, or emission properties. Polyoxometalate crystals hybridized with surfactant cations have distinct layered packings due to the surfactants which can form lamellar structures. Introducing metal cations into such polyoxometalate-surfactant hybrid crystals is significant for the addition of specific functions. Here, polyoxomolybdate–surfactant hybrid crystals were synthesized as single crystals, and unambiguously characterized by X-ray structure analyses. Octamolybdate ([Mo8O26]4–, Mo8) and heterocyclic surfactant of 1-dodecylpyridinium (C12py) were employed. The hybrid crystals were composed of α-type and β-type Mo8 isomers. Two crystalline phases containing α-type Mo8 were obtained as pseudopolymorphs depending on the crystallization conditions. Crystallization with the presence of rubidium and cesium cations caused the formation of metal cation-introduced hybrid crystals comprising β-Mo8 (C12py-Rb-Mo8 and C12py-Cs-Mo8). The yield of the C12py-Rb-Mo8 hybrid crystal was almost constant within crystallization temperatures of 279–303 K, while that of C12py-Cs-Mo8 decreased over 288 K. This means that the C12py-Mo8 hybrid crystal can capture Rb+ and Cs+ from the solution phase into the solids as the C12py-Rb-Mo8 and C12py-Cs-Mo8 hybrid crystals. The C12py-Mo8 hybrid crystals could be applied to ion-capturing materials for heavy metal cation removal. Full article
(This article belongs to the Special Issue Inorganic Metal-to-Ligand Clusters)
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