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Organometallic Compounds and Their Applications
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Organometallic Compounds and Their Applications

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

Deadline for manuscript submissions: closed (21 October 2021) | Viewed by 11054

Special Issue Editor

Prof. Dr. Elena V. Grachova

E-Mail Website
Guest Editor
Saint Petersburg State University, Saint Petersburg (ex Leningrad), St. Petersburg, Russia
Interests: coordination chemistry; organometallic chemistry; transition metal cluster compounds; nano-scale molecular ensembles; supramolecular compounds; metal-containing molecular entities and materials; molecular emitters

Special Issue Information

Dear Colleagues,

Organometallic compounds (OMCs) play a critical role in modern chemical science and are used in many areas of chemistry, not only as fundamental research objects but for a variety of practical applications. It is impossible to imagine most catalytic processes in modern organic and organoelement chemistry without OMCs, and using OMCs as catalysts and photocatalysts is a huge field of application but does not limit it. Luminescent OMCs are widely used to create electroluminescent devices, and for the design of labels for visualization of biological structures and processes, fluorescent sensors for precision measurement of temperature and pH, oxygen mapping, drug delivery tracing, generation of singlet oxygen, sensing of different ions in the solution, and sensing of small molecules, including explosive substances. OMCs play an undoubtable role in the problem of solar energy conversion and light harvesting processes, creation of materials for photonics and non-linear optics, design of information storage and transfer systems, and design of metallomesogens, molecular magnets, and magnetic materials. OMCs can be used as building blocks for the construction of cage compounds, coordination polymers, MOFs, supramolecular systems, and as sources for nanostructured materials and nano-hybrid composites.

Thus, this Special Issue is intended to illustrate the key role of OMCs in innovative applications and to give readers an opportunity to look at OMCs not only as interesting molecules, but also as the crucial link in the chain between a chemical idea and its practical implementation in various chemical contexts.

Communications, articles, and reviews on the abovementioned topics are welcome.

Prof. Dr. Elena V. Grachova
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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. Molecules 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 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

  • organometallic compound
  • transition metal
  • lanthanide
  • homogeneous catalysis
  • photocatalysis
  • molecular emitter
  • bio-imaging
  • electroluminescence
  • sensing
  • energy conversion
  • light harvesting
  • magnetism
  • photonics
  • coordination polymer
  • metal–organic framework
  • stimuli-responsive

Published Papers (5 papers)

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Research

14 pages, 2525 KiB  
Article
From a Well-Defined Organozinc Precursor to Diverse Luminescent Coordination Polymers Based on Zn(II)-Quinolinate Building Units Interconnected by Mixed Ligand Systems
by Katarzyna Sołtys-Brzostek, Kamil Sokołowski, Iwona Justyniak, Michał K. Leszczyński, Natalia Olejnik-Fehér and Janusz Lewiński
Molecules 2021, 26(23), 7402; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26237402 - 06 Dec 2021
Cited by 1 | Viewed by 1721
Abstract
Introduction of photoactive building blocks into mixed-ligand coordination polymers appears to be a promising way to produce new advanced luminescent materials. However, rational design and self-assembly of the multi-component supramolecular systems is challenging from both a conceptual and synthetic perspective. Here, we report [...] Read more.
Introduction of photoactive building blocks into mixed-ligand coordination polymers appears to be a promising way to produce new advanced luminescent materials. However, rational design and self-assembly of the multi-component supramolecular systems is challenging from both a conceptual and synthetic perspective. Here, we report exploratory studies that investigate the potential of [Zn(q)2]2[tBuZn(OH)]2 complex (q = deprotonated 8-hydroxyquinoline) as an organozinc precursor as well as a mixed-ligand synthetic strategy for the preparation of new luminescent coordination polymers (CPs). As a result we present three new 2D mixed-ligand Zn(II)-quinolinate coordination polymers which are based on various zinc quinolinate secondary building units interconnected by two different organic linker types, i.e., deprotonated 4,4′-oxybisbenzoic acid (H2obc) as a flexible dicarboxylate linker and/or selected bipyridines (bipy). Remarkably, using the title organozinc precursors in a combination with H2obc and 4,4′-bipyridine, a novel molecular zinc quinolinate building unit, [Zn4(q)6(bipy)2(obc)2], was obtained which self-assembled into a chain-type hydrogen-bonded network. The application of the organometallic precursor allowed for its direct reaction with the selected ligands at ambient temperature, avoiding the use of both solvothermal conditions and additional base reagents. In turn, the reaction involving Zn(NO3)2, as a classical inorganic precursor, in a combination with H2obc and bipy led to a novel 1D coordination polymer [Zn2(q)2(NO3)2(bipy)]. While the presence of H2obc was essential for the formation of this coordination polymer, this ditopic linker was not incorporated into the isolated product, which indicates its templating behavior. The reported compounds were characterized by single-crystal and powder X-ray diffraction, elemental analysis as well as UV-Vis and photoluminescence spectroscopy. Full article
(This article belongs to the Special Issue Organometallic Compounds and Their Applications)
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13 pages, 1844 KiB  
Article
Dipyridylmethane Ethers as Ligands for Luminescent Ir Complexes
by Giorgio Volpi, Claudio Garino, Roberto Gobetto and Carlo Nervi
Molecules 2021, 26(23), 7161; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26237161 - 26 Nov 2021
Cited by 2 | Viewed by 1438
Abstract
This work reports two new cationic heteroleptic cyclometalated iridium complexes, containing ether derivatives of di(pyridin-2-yl)methanol. The new ligands are based on dipyridin-2-ylmethane and are designed to obtain ether-based intermediates with extended electronic conjugation by insertion of π system such as phenyl, allyl and [...] Read more.
This work reports two new cationic heteroleptic cyclometalated iridium complexes, containing ether derivatives of di(pyridin-2-yl)methanol. The new ligands are based on dipyridin-2-ylmethane and are designed to obtain ether-based intermediates with extended electronic conjugation by insertion of π system such as phenyl, allyl and ethynyl. Different synthetic strategies were employed to introduce these units, as molecular wires, between the dipyridin-2-ylmethane chelating portion and the terminal N-containing functional group, such as amine and carbamide. The corresponding complexes show luminescence in the blue region of the spectrum, lifetimes between 0.6 and 2.1 μs, high quantum yield and good electrochemical behavior. The computational description (DFT) of the electronic structure highlights the key role of the conjugated π systems on optical and electrochemical properties of the final products. Full article
(This article belongs to the Special Issue Organometallic Compounds and Their Applications)
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11 pages, 2605 KiB  
Article
Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers
by Egor M. Baranovskii, Victoria V. Khistiaeva, Konstantin V. Deriabin, Stanislav K. Petrovskii, Igor O. Koshevoy, Ilya E. Kolesnikov, Elena V. Grachova and Regina M. Islamova
Molecules 2021, 26(22), 6866; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26226866 - 14 Nov 2021
Cited by 5 | Viewed by 1819
Abstract
This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction [...] Read more.
This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N3-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)3(MeCN)(5-(4-ethynylphenyl)-2,2′-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N3-PDMS (Re1-PDMS), while [Re(CO)3Cl(5,5′-diethynyl-2,2′-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N3-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties. Full article
(This article belongs to the Special Issue Organometallic Compounds and Their Applications)
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21 pages, 4816 KiB  
Article
Preparation of High-Purity Ammonium Tetrakis(pentafluorophenyl)borate for the Activation of Olefin Polymerization Catalysts
by Hyun-Ju Lee, Jun-Won Baek, Yeong-Hyun Seo, Hong-Cheol Lee, Sun-Mi Jeong, Junseong Lee, Chong-Gu Lee and Bun-Yeoul Lee
Molecules 2021, 26(9), 2827; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26092827 - 10 May 2021
Cited by 6 | Viewed by 2973
Abstract
Homogeneous olefin polymerization catalysts are activated in situ with a co-catalyst ([PhN(Me)2-H]+[B(C6F5)4]− or [Ph3C]+[B(C6F5)4]−) in bulk polymerization media. These co-catalysts [...] Read more.
Homogeneous olefin polymerization catalysts are activated in situ with a co-catalyst ([PhN(Me)2-H]+[B(C6F5)4]− or [Ph3C]+[B(C6F5)4]−) in bulk polymerization media. These co-catalysts are insoluble in hydrocarbon solvents, requiring excess co-catalyst (>3 eq.). Feeding the activated species as a solution in an aliphatic hydrocarbon solvent may be advantageous over the in situ activation method. In this study, highly pure and soluble ammonium tetrakis(pentafluorophenyl)borates ([Me(C18H37)2N-H]+[B(C6F5)4]− and [(C18H37)2NH2]+[B(C6F5)4]−) containing neither water nor Cl− salt impurities were prepared easily via the acid–base reaction of [PhN(Me)2-H]+[B(C6F5)4]− and the corresponding amine. Using the prepared ammonium salts, the activation reactions of commercial-process-relevant metallocene (rac-[ethylenebis(tetrahydroindenyl)]Zr(Me)2 (1-ZrMe2), [Ph2C(Cp)(3,6-tBu2Flu)]Hf(Me)2 (3-HfMe2), [Ph2C(Cp)(2,7-tBu2Flu)]Hf(Me)2 (4-HfMe2)) and half-metallocene complexes ([(η5-Me4C5)Si(Me)2(κ-NtBu)]Ti(Me)2 (5-TiMe2), [(η5-Me4C5)(C9H9(κ-N))]Ti(Me)2 (6-TiMe2), and [(η5-Me3C7H1S)(C10H11(κ-N))]Ti(Me)2 (7-TiMe2)) were monitored in C6D12 with 1H NMR spectroscopy. Stable [L-M(Me)(NMe(C18H37)2)]+[B(C6F5)4]− species were cleanly generated from 1-ZrMe2, 3-HfMe2, and 4-HfMe2, while the species types generated from 5-TiMe2, 6-TiMe2, and 7-TiMe2 were unstable for subsequent transformation to other species (presumably, [L-Ti(CH2N(C18H37)2)]+[B(C6F5)4]−-type species). [L-TiCl(N(H)(C18H37)2)]+[B(C6F5)4]−-type species were also prepared from 5-TiCl(Me) and 6-TiCl(Me), which were newly prepared in this study. The prepared [L-M(Me)(NMe(C18H37)2)]+[B(C6F5)4]−-, [L-Ti(CH2N(C18H37)2)]+[B(C6F5)4]−-, and [L-TiCl(N(H)(C18H37)2)]+[B(C6F5)4]−-type species, which are soluble and stable in aliphatic hydrocarbon solvents, were highly active in ethylene/1-octene copolymerization performed in aliphatic hydrocarbon solvents. Full article
(This article belongs to the Special Issue Organometallic Compounds and Their Applications)
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12 pages, 2890 KiB  
Article
Effect of Substituents of Cerium Pyrazolates and Pyrrolates on Carbon Dioxide Activation
by Uwe Bayer, Adrian Jenner, Jonas Riedmaier, Cäcilia Maichle-Mössmer and Reiner Anwander
Molecules 2021, 26(7), 1957; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26071957 - 31 Mar 2021
Cited by 2 | Viewed by 1962
Abstract
Homoleptic ceric pyrazolates (pz) Ce(RR’pz)4 (R = R’ = tBu; R = R’ = Ph; R = tBu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe2)2]4 with the corresponding pyrazole derivative. The [...] Read more.
Homoleptic ceric pyrazolates (pz) Ce(RR’pz)4 (R = R’ = tBu; R = R’ = Ph; R = tBu, R’ = Me) were synthesized by the protonolysis reaction of Ce[N(SiHMe2)2]4 with the corresponding pyrazole derivative. The resulting complexes were investigated in their reactivity toward CO2, revealing a significant influence of the bulkiness of the substituents on the pyrazolato ligands. The efficiency of the CO2 insertion was found to increase in the order of tBu2pz < Ph2pz < tBuMepz < Me2pz. For comparison, the pyrrole-based ate complexes [Ce2(pyr)6(µ-pyr)2(thf)2][Li(thf)4]2 (pyr = pyrrolato) and [Ce(cbz)4(thf)2][Li(thf)4] (cbz = carbazolato) were obtained via protonolysis of the cerous ate complex Ce[N(SiHMe2)2]4Li(thf) with pyrrole and carbazole, respectively. Treatment of the pyrrolate/carbazolate complexes with CO2 seemed promising, but any reversibility could not be observed. Full article
(This article belongs to the Special Issue Organometallic Compounds and Their Applications)
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