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Inorganics
Special Issues
Heterometallic Complexes
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Heterometallic Complexes

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (15 December 2022) | Viewed by 10435

Special Issue Editors

Prof. Dr. Daniel García‐Vivó

E-Mail Website
Guest Editor
Departamento de Química Orgánica e Inorgánica/IUQOEM, Universidad de Oviedo, E-33071 Oviedo, Spain
Interests: organometallic chemistry; transition metal carbonyls; metal–metal bonding; P-ligands; DFT calculations
Prof. Dr. Marius Andruh

E-Mail Website
Guest Editor
1. Laboratory of Inorganic Chemistry, Faculty of Chemistry, University of Bucharest, Bd. Regina Elisabeta nr. 4-12, Bucharest, Romania
2. "C. D. Nenitzescu" Institute of Organic and Supramolecular Chemistry of the Romanian Academy, Splaiul Independentei 202 B, Bucharest, Romania
Interests: molecular magnetism; crystal engineering; metallosupramolecular chemistry; homo- and hetero-polynuclear complexes
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The synthesis and chemical study of polymetallic compounds has been a relevant topic in different areas of Inorganic and Organometallic Chemistry over the past decades, mainly as consequence of their potential application in homo- and heterogeneous catalysis, but also for the novel electronic or magnetic properties that these compounds can display. Polynuclear complexes containing two or more different paramagnetic ions are of high interest in molecular magnetism. Numerous Single Molecule Magnets (SMMs) and Single Chain Magnets (SCMs), and most of the 3D molecule-based magnets are heterometallic complexes. Of particular interest are the Metal–Organic Frameworks (MOFs) constructed from different metallic nodes. Various applications for MOFs have been envisioned: separation and storage of specific molecules, catalysis, multifunctional materials, etc. The close proximity of the metals in these systems lies at the heart of their enhanced properties, as it allows the metals to act through cooperative and synergistic pathways that are impossible for related mononuclear complexes. Typically, the approximation of the metals is achieved by the presence of direct metal-metal bonds or by using suitable bridging ligands, which can also provide additional stability to the system. In search of new properties and/or better catalytic activities, a natural extension of these works that gained tremendous interest recently is the preparation of heterometallic complexes bearing different metal atoms. There are several appealing reasons for the renewed interest in this area. Firstly, in nature, several natural enzymes are based on electron transfer steps taking place at different metal atoms held together by the enzyme backbone, and this has prompted interest in preparing molecular mimics capable of accomplishing similar processes. Secondly, the different electronic and coordinative preferences of two different metals can give rise to chemical properties and reactivity departing significantly from those of each isolated fragment. Thirdly, there is a fundamental interest in the study of new M-M′ bonding interactions, especially for multiply bonded systems. Finally, tandem processes might also benefit from the combined presence of two different metals in a complex, with each metal completing specifically one elementary transformation as part of a more complex process.

This Special Issue of Inorganics, entitled “Heterometallic Complexes”, will deal with the new synthetic methods developed for the preparation of heterometallic complexes, but also with aspects such as the collection of new structural information, the analysis of their electronic structure, and the bonding or the development of novel applications in catalysis and beyond.

Prof. Dr. Daniel García‐Vivó
Prof. Dr. Marius Andruh
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. Inorganics is an international peer-reviewed open access monthly 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 2700 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

  • heterometallic compounds
  • polynuclear compounds
  • metal–metal bonding
  • small molecule activation
  • electronic structure
  • molecular magnetism
  • tandem catalysis

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Published Papers (3 papers)

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Research

13 pages, 2424 KiB  
Article
Synthesis of a Heterometallic [Zn2Ca] Pinwheel Array Stabilized by Amide-Amide Synthons
by Daniel Ejarque, Teresa Calvet, Mercè Font-Bardia and Josefina Pons
Inorganics 2022, 10(8), 118; https://doi.org/10.3390/inorganics10080118 - 14 Aug 2022
Cited by 2 | Viewed by 2293
Abstract
The rational design of heterometallic compounds bearing s-block metal ions have been a difficult task for chemists owing to their lack of preferential geometries. However, some strategies, such as the design of coordinating pockets with different sizes and/or donor atoms, have offered great [...] Read more.
The rational design of heterometallic compounds bearing s-block metal ions have been a difficult task for chemists owing to their lack of preferential geometries. However, some strategies, such as the design of coordinating pockets with different sizes and/or donor atoms, have offered great results. In this work, this strategy has been tested using Ca(II) as an s-block metal ion and a compound previously obtained by our group with the formula [Zn3(μ-ACA)6(4-phpy)2], which contains tetrahedral N,O- and octahedral O-coordinating pockets as a model structure. From this work, the corresponding heterometallic compound with the formula [Zn2Ca(μ-ACA)6(4-phpy)2]·EtOH (1) has been successfully synthesized, and fully characterized, and its crystal structure has been elucidated. Furthermore, we have compiled all the crystal structures containing [Zn2M] pinwheel secondary building units (SBUs), where M stands for an s-block metal ion, and the observed tendencies, as well as the promising applications as template SBUs for the preparation of 1D–3D coordination polymers, have been discussed. Finally, solid-state UV-Vis and photoluminescence have been recorded and compared with the homometallic [Zn3(μ-ACA)6(4-phpy)2] compound. Full article
(This article belongs to the Special Issue Heterometallic Complexes)
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15 pages, 6544 KiB  
Article
Influence of Substituents in Terephthalate Linker on the Structure of MOFs Obtained from Presynthesized Heterometallic Complex
by Marina Barsukova, Evgeny Dudko, Denis Samsonenko, Konstantin Kovalenko, Alexey Ryadun, Aleksandr Sapianik and Vladimir Fedin
Inorganics 2021, 9(1), 4; https://doi.org/10.3390/inorganics9010004 - 2 Jan 2021
Cited by 1 | Viewed by 3152
Abstract
The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic [...] Read more.
The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic frameworks could be essential to solve the problem of tailored synthesis. In our study we use presynthesized heterometallic pivalate complex [Li2Zn2(piv)6(py)2] to obtain new MOFs with heterometallic core as a node of the framework. We are managed to obtain four new heterometallic MOFs: [H2N(CH3)2]2[Li2Zn2(bdc)4]·CH3CN·DMF (1), [Li2Zn2(H2Br2-bdc)(Br2-bdc)3]·2DMF (2), [H2N(CH3)2][LiZn2(ndc)3]·CH3CN (3) and [{Li2Zn2(dmf)(py)2}{LiZn(dmf)2}2 (NO2-bdc)6]·5DMF (4). Moreover three of them contain starting tetranuclear core {Li2Zn2} and saves its geometry. We also demonstrate the influence of substituent in terephthalate ring on preservation of tetranuclear core. For compound 1 it was shown that luminescence of the framework could be quenched when nitrobenzene is included in the pores. Full article
(This article belongs to the Special Issue Heterometallic Complexes)
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11 pages, 1098 KiB  
Article
Heterobimetallic Chromium Manganese Carbonyl Nitrosyls: Comparison with Isoelectronic Homometallic Binuclear Chromium Carbonyl Nitrosyls and Manganese Carbonyls
by Guoliang Li, Limei Wen and R. Bruce King
Inorganics 2019, 7(10), 127; https://doi.org/10.3390/inorganics7100127 - 21 Oct 2019
Viewed by 3322
Abstract
The heterometallic chromium-manganese carbonyl nitrosyls CrMn(NO)(CO)n (n = 9, 8) have been investigated by density functional theory. The lowest energy CrMn(NO)(CO)9 structures have unbridged staggered conformations with a ~2.99 Å Cr–Mn single bond similar to the experimental and lowest energy [...] Read more.
The heterometallic chromium-manganese carbonyl nitrosyls CrMn(NO)(CO)n (n = 9, 8) have been investigated by density functional theory. The lowest energy CrMn(NO)(CO)9 structures have unbridged staggered conformations with a ~2.99 Å Cr–Mn single bond similar to the experimental and lowest energy structures of the isoelectronic Mn2(CO)10 and Cr2(NO)2(CO)8. A significantly higher energy CrMn(NO)(CO)9 isomer has a nearly symmetrical bridging nitrosyl group and a very weakly semibridging carbonyl group. The two lowest energy structures of the unsaturated CrMn(NO)(CO)8 have a five-electron donor bridging η2-µ-NO nitrosyl group or a four-electron donor bridging η2-µ-CO group, as well as a Cr–Mn single bond of length ~2.94 Å. The next higher energy CrMn(NO)(CO)8 structure has exclusively terminal CO and NO ligands and a shorter Cr–Mn single bond of ~2.85 Å, suggesting an 18-electron configuration for the manganese atom and a 16-electron configuration for the chromium atom indicated by a vacant coordination site nearly perpendicular to the Cr–Mn bond. Full article
(This article belongs to the Special Issue Heterometallic Complexes)
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