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Inorganics
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10th Anniversary of Inorganics: Organometallic Chemistry
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10th Anniversary of Inorganics: Organometallic Chemistry

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

Deadline for manuscript submissions: closed (31 October 2023) | Viewed by 36309

Special Issue Editors

Prof. Dr. Francis Verpoort

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State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430000, China
Interests: organometallics; metal-organic frameworks; porous organic polymers; electrocatalysis; photocatalysis; thermocatalysis; reaction mechanisms; metal-organic framework derivatives; clean energy technologies; environmental applications; water splitting; fuel cells; organic catalysis; CO2 capture
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Prof. Dr. Claudio Pettinari

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1. Chemistry Center, School of Pharmacy, Camerino, University of Camerino, Via Madonna delle Carceri, 62032 Camerino, Italy
2. CNR ICCOM, 50019 Sesto Fiorentino, Italy
3. IUSS Pavia, 27100 Pavia, Italy
Interests: metal-organic frameworks (MOFs); antitumoral compounds; antitbacterial compounds; H2 storage, CO2 storage and transformation, metal-catalyzed oxidations
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Dr. Maurizio Peruzzini

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Consiglio Nazionale delle Ricerche (CNR) Istituto di Chimica dei Composti OrganoMetallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, FI, Italy
Interests: activation and functionalization of elemental phosphorus; activation of small inorganic and organic molecules; transition-metal hydrides and molecular hydrogen chemistry; materials for H-storage; carbon dioxide capture and valorization
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Prof. Dr. Richard Layfield

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Department of Chemistry, School of Life Sciences, University of Sussex, Falmer, Brighton BN1 9QJ, UK
Interests: organometallic chemistry; lanthanides; molecular magnetism; low-coordinate transition metal chemistry
Prof. Dr. Rainer Winter

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Department of Chemistry, Universitat Konstanz, 78464 Konstanz, Germany
Interests: organometallic chemistry; ruthenium complexes; (spectro)electrochemistry; metallocenes; valence tautomerism; mixed-valent chemistry; luminescent platinum complexes; metallamacrocyclic complexes
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Prof. Dr. Moris S. Eisen

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Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 3200008, Israel
Interests: actinide and lanthanide organometallic chemistry; polymerization catalysis; organo-f-complexes in catalysis; small molecule activation; transition metal organometallic chemistry; metal-ligand multiple bonding; group 4 organometallics in catalysis
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Dr. Gábor Papp

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Department of Physical Chemistry, University of Debrecen, 4032 Debrecen, Hungary
Interests: hydrogenation; dehydrogenation; para-hydrogen; hydrogen storage; aqueous media
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Dr. Shuang Xiao

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Shenzhen Key Laboratory of Ultraintense Laser and Advanced Material Technology, Center for Intense Laser Application Technology (iLaT) and College of Engineering Physics, Shenzhen Technology University, Shenzhen 518118, China
Interests: organometal halide perovskite; photovoltaics; radiation detection
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Prof. Dr. Axel Klein

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Faculty of Mathematics and Natural Sciences, Department of Chemistry, Institute for Inorganic Chemistry, University of Cologne, Greinstraße 6, 50939 Köln, Germany
Interests: coordination chemistry; organometallics; catalysis; transition metals; photophysics; electrochemistry
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Special Issue Information

Dear Colleagues,

Organometallic chemistry has become an impactful area of chemistry and is employed in many areas of chemistry. Organometallic chemistry is now as vibrant and exciting as ever, with research impacting photo-, electro-, and thermal catalysis, main-group chemistry, chemical biology, lanthanides and actinides, organic synthesis, and materials science. For instance, luminescent organometallic compounds are broadly used to produce electroluminescent devices, fluorescent sensors, and labels for the visualization of biological structures and processes and in oxygen mapping and generation of singlet oxygen, drug delivery tracking, sensing of different ions in the solution, and sensing of small molecules. There is no limit to the applications of organometallic chemistry. Organometallic chemistry is involved in constructing cage compounds, coordination polymers, MOFs, supramolecular systems, nanostructured materials, nanotechnology, molecular magnets, and many more.

Hence, this Special Issue, celebrating the 10th Anniversary of Inorganics intends to bring the role of organometallic chemistry and related applications into the spotlight, thus allowing readers to appreciate organometallic chemistry as a paramount area of chemical sciences that is intertwined with many other fields ranging from industrial to medical applications to nanotechnology. This Special Issue offers the unique opportunity for exchange between scientists and researchers in organometallic chemistry in mostly chemistry (inorganic and organic), (bio)medicinal chemistry, polymer chemistry, metallocene, industrial chemistry, catalysis, material, and nanotech fields. Communications, original research and comprehensive review papers, and perspectives contributing to the field are welcome.

Prof. Dr. Francis Verpoort
Prof. Dr. Claudio Pettinari
Prof. Dr. Maurizio Peruzzini
Prof. Dr. Richard Layfield
Prof. Dr. Rainer Winter
Prof. Dr. Moris S. Eisen
Dr. Gábor Papp
Prof. Dr. Shuang Xiao
Prof. Dr. Axel Klein
Guest Editors

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Keywords

  • organometallic compounds
  • transition metals
  • lanthanides
  • actinides
  • main group elements
  • organometallic compounds in catalysis
  • organometallic compounds in photocatalysis
  • organometallic compounds in electrocatalysis
  • organometallic compounds in thermocatalysis
  • organometallic compounds as molecular emitters
  • organometallic compounds in bio-imaging
  • organometallic compounds in electroluminescence
  • organometallic compounds in sensing
  • organometallic compounds in energy conversion
  • organometallic compounds in light harvesting
  • organometallic compounds in magnetism
  • organometallic compounds in photonics
  • organometallic compounds in coordination polymer
  • organometallic compounds in metal–organic framework
  • organometallic compounds in materials science
  • organometallic compounds in supramolecular chemistry and in crystal engineering
  • computational/theoretical organometallic chemistry
  • further areas for development and new perspectives

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Published Papers (13 papers)

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18 pages, 4425 KiB  
Article
Investigations of the Influence of Two Pyridyl-Mesoionic Carbene Constitutional Isomers on the Electrochemical and Spectroelectrochemical Properties of Group 6 Metal Carbonyl Complexes
by Tobias Bens and Biprajit Sarkar
Inorganics 2024, 12(2), 46; https://doi.org/10.3390/inorganics12020046 - 29 Jan 2024
Cited by 1 | Viewed by 2037
Abstract
Metal complexes of mesoionic carbenes (MICs) of the triazolylidene type and their derivatives have gained increasing attention in the fields of electrocatalysis and photochemistry. The redox activity of these metal complexes is critical for their applications in both the aforementioned fields. Easy accessibility [...] Read more.
Metal complexes of mesoionic carbenes (MICs) of the triazolylidene type and their derivatives have gained increasing attention in the fields of electrocatalysis and photochemistry. The redox activity of these metal complexes is critical for their applications in both the aforementioned fields. Easy accessibility and modular synthesis open a wide field for the design of ligands, such as bidentate ligands. The combination of an MIC with a pyridyl unit in a bidentate ligand setup increases the π acceptor properties of the ligands while retaining their strong σ donor properties. The analogy with the well-established 2,2′-bipyridine ligand allows conclusions to be drawn about the influence of the mesoionic carbene (MIC) moiety in tetracarbonyl group 6 complexes in cyclic voltammetry and (spectro)electrochemistry (SEC). However, the effects of the different connectivity in pyridyl-MIC ligands remain underexplored. Based on our previous studies, we present a thorough investigation of the influence of the two different pyridyl-MIC constitutional isomers on the electrochemical and the UV-vis-NIR/IR/EPR spectroelectrochemical properties of group 6 carbonyl complexes. Moreover, the presented complexes were investigated for the electrochemical conversion of CO2 using two different working electrodes, providing a fundamental understanding of the influence of the electrode material in the precatalytic activation. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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18 pages, 3008 KiB  
Article
Organoplatinum Chemistry Related to Alkane Oxidation: The Effect of a Nitro Substituent in Ligands Having an Appended Phenol Group
by Anwar Abo-Amer, Mohamed E. Moustafa, Paul D. Boyle and Richard J. Puddephatt
Inorganics 2024, 12(1), 32; https://doi.org/10.3390/inorganics12010032 - 16 Jan 2024
Cited by 1 | Viewed by 2427
Abstract
The organoplatinum chemistry of the ligands 2-C5H4N-CH2-NH-C6H3-2-OH-5-X (L1, X = H; L3, X = NO2) and 2-C5H4N-CH=N-C6H3-2-OH-5-X (L2, [...] Read more.
The organoplatinum chemistry of the ligands 2-C5H4N-CH2-NH-C6H3-2-OH-5-X (L1, X = H; L3, X = NO2) and 2-C5H4N-CH=N-C6H3-2-OH-5-X (L2, X = H; L4, X = NO2), which contain an appended phenol substituent, is described. Comparisons are made between the ligands with amine or imine groups (L1, L3 vs. L2, L4) and ligands with X = H or NO2 (L1, L2 vs. L3, L4), and major differences are observed. Thus, on reaction with the cycloneophylplatinum(II) complex [{Pt(CH2CMe2C6H4)(μ-SMe2)}2], ligands L1, L2 and L4 give the corresponding platinum(II) complexes [Pt(CH2CMe2C6H4)(κ2-N,N′-L)], containing a Pt··HO hydrogen bond, whereas L3 gives a mixture of isomeric platinum(IV) hydride complexes [PtH(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)], which are formed by oxidative addition of the phenol O-H bond and which react further with oxygen to give [Pt(OH)(CH2CMe2C6H4)(κ3-N,N′,O-L3-H)]. The differences in reactivity are proposed to be due to the greater acidity of the nitro-substituted phenol groups in L3 and L4 and to the greater ability of the deprotonated amine ligand L3 over L4 to stabilize platinum(IV) by adopting the fac-κ3-N,N′,O-L3-H coordination mode. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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26 pages, 7229 KiB  
Article
Probing the Electronic Structure of Dinuclear Carbon-Rich Complexes Containing an Octa-3,5-diene-1,7-diyndiyl Bridging Ligand
by Michael R. Hall, Stephen A. Moggach and Paul J. Low
Inorganics 2024, 12(1), 20; https://doi.org/10.3390/inorganics12010020 - 1 Jan 2024
Viewed by 2517
Abstract
One electron oxidation of the monometallic alkenylacetylide complexes [Ru{C≡CC(R)=CH2}(dppe)Cp*] (1) and [Ru{C≡CC(R)=CH2}Cl(dppe)2] (2) (R = Ph (a); R = 4-MeS-C6H4 (b)) generates in each case a [...] Read more.
One electron oxidation of the monometallic alkenylacetylide complexes [Ru{C≡CC(R)=CH2}(dppe)Cp*] (1) and [Ru{C≡CC(R)=CH2}Cl(dppe)2] (2) (R = Ph (a); R = 4-MeS-C6H4 (b)) generates in each case a dinuclear bis(allenylidene) complex [{Ru}2{μ-C=C=C(R)–CH2–H2C–(R)C=C=C}][PF6]2 ({Ru} = Ru(dppe)Cp* ([3a,b][PF6]2); {Ru} = RuCl(dppe)2 ([4a,b][PF6]2), containing an unsaturated ethane bridge between both allenylidene moieties. Deprotonation of this ethane bridge results in the formation of the previously reported octa-3,5-diene-1,7-diyndiyl-bridged bimetallic species [{Ru}2{μ-C≡CC(R)=CH–HC=(R)CC≡C}] ({Ru} = Ru(dppe)Cp* (5a,b); {Ru} = RuCl(dppe)2 (6a,b). The isolation of these complexes illustrates a general synthetic route to these conjugated bimetallic species from monomeric alkenylacetylide precursors. Electrochemical and spectroelectrochemical investigations evince the ready formation of the representative redox series [5a]n+, and TD-DFT calculations performed on optimised structures featuring the simplified {Ru(dmpe)Cp} coordination sphere [{Ru(dmpe)Cp}2{μ-C≡CC(Ph)=HC–CH(Ph)CC≡C}]n+ ([5a†]n+) (n = 0, 1, 2) reveal significant delocalisation of the unpaired charge in the formally mixed-valent species (n = 1), consistent with Class III assignment within the Robin–Day classification scheme. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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21 pages, 2446 KiB  
Article
A Model Halogen-Bonded Network as a Potential Tube-like Host for Li+: A DFT Study
by Rubén D. Parra
Inorganics 2024, 12(1), 16; https://doi.org/10.3390/inorganics12010016 - 30 Dec 2023
Cited by 2 | Viewed by 2319
Abstract
The formation of a halogen-bonded network using four NHX-(CH2)3-NX-(CH2)3-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C4h [...] Read more.
The formation of a halogen-bonded network using four NHX-(CH2)3-NX-(CH2)3-NHX molecules (X = Cl, Br, or I) is investigated using DFT. The self-assembly of the four basic motifs results in a tube-like structure with C4h symmetry, with one halogen-bonded network located at each end of the structure and one at its center. Each halogen-bonded network has four quasi-planar N-X···N interactions with binding energies that increase with the size of X. The structure is found to bind Li+ at each of the halogen-bonded networks, albeit more strongly at its center. The binding of Li+ is driven by halogen atom lone pairs that produce a rich electron density orthogonal to the halogen bond. The presence and strength of the interactions are further examined using AIM and NBO calculations. Lastly, IRC calculations are performed to examine the transitions between the Li+ complex minima and, thus, the potential for transporting the metal ion from one end of the tube to the other. Based on the tetrameric structure, a model intramolecular structure is built and considered as a potential host for Li+. In this case, the central intermolecular N-X···N network is replaced by an intramolecular Si-C≡C-Si network. Interestingly, both intermolecular and intramolecular structures exhibit similar Li+ binding abilities. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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13 pages, 3336 KiB  
Article
Modulation of Ferrocene–Ferrocene Interactions by Varying Their Reciprocal Positions in L-Dap/Aib Helical Peptides
by Annalisa Bisello, Barbara Biondi, Roberta Cardena, Renato Schiesari, Marco Crisma, Fernando Formaggio and Saverio Santi
Inorganics 2023, 11(12), 482; https://doi.org/10.3390/inorganics11120482 - 16 Dec 2023
Cited by 1 | Viewed by 1887
Abstract
In this work, we developed two new polyfunctional hybrid systems in which the presence of Fc redox “antennas” on peptide scaffolds allows for a modulation of their electronic properties. Specifically, we synthesized two helical hexapeptides containing four Aib (α-amionoisobutyric acid) and two L [...] Read more.
In this work, we developed two new polyfunctional hybrid systems in which the presence of Fc redox “antennas” on peptide scaffolds allows for a modulation of their electronic properties. Specifically, we synthesized two helical hexapeptides containing four Aib (α-amionoisobutyric acid) and two L-Dap (2,3-diamino propionic acid) residues. L-Dap side chains were then functionalized with Fc moieties. The structures of the two 310 helical peptides, namely Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr and Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, were investigated by X-ray diffraction, 2D-NMR, CD and IR spectroscopies. Due to the helical conformation, in Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr, the Fc groups are located on the same face of the helix, but in Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, they are located on opposite faces. Surprisingly, two bands were found through DPV for Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, indicating an electrostatic interaction between the Fc groups despite their longer reciprocal distance with respect to that in Z-Aib-L-Dap(Fc)-Aib-Aib-L-Dap(Fc)-Aib-NH-iPr. CD experiments at different concentrations evidenced aggregation for Z-Aib-L-Dap(Fc)-Aib-L-Dap(Fc)-Aib-Aib-NH-iPr, even at high dilutions, thus suggesting that the Fc-Fc electrostatic interaction could be of an intermolecular nature. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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20 pages, 7335 KiB  
Article
Valence Tautomerism in Chromium Half-Sandwich Triarylmethylium Dyads
by Anja Rehse, Michael Linseis, Mykhailo Azarkh, Malte Drescher and Rainer F. Winter
Inorganics 2023, 11(11), 448; https://doi.org/10.3390/inorganics11110448 - 20 Nov 2023
Viewed by 2121
Abstract
Valence tautomerism (VT) may occur if a molecule contains two chemically different redox-active units, which differ only slightly in their intrinsic redox potential. Herein, we present three new half-sandwich complexes [(η6-arene)Cr(CO)2L]+ with a triarylmethylium substituent appended to [...] Read more.
Valence tautomerism (VT) may occur if a molecule contains two chemically different redox-active units, which differ only slightly in their intrinsic redox potential. Herein, we present three new half-sandwich complexes [(η6-arene)Cr(CO)2L]+ with a triarylmethylium substituent appended to the π-coordinated arene and different coligands L (L = CO, P(OPh)3, PPh3, 1+–3+) at the chromium atom. Ligand substitution purposefully lowers the half-wave potential for chromium oxidation and thereby the redox potential difference towards tritylium reduction. For the PPh3-substituted complex 3+, cyclic voltammetry measurements indicate that chromium oxidation and tritylium reduction occur at (almost) the same potential. This renders the diamagnetic Cr(0)-C6H4-CAr2+ form 3+, and its paramagnetic diradical Cr(I)+•-C6H4-CAr2• valence tautomer 3+•• energetically nearly degenerate. Temperature-dependent IR spectroscopy indeed shows two pairs of carbonyl bands that are assignable to a Cr(0) and a Cr(I) species, coexisting in a T-dependent equilibrium with almost equal quantities for both at −70 °C. The diradical form with one unpaired spin at the trityl unit engages in a monomer ⇌ dimer equilibrium, which was investigated by means of quantitative EPR spectroscopy. The diradical species 1+••–3+•• were found to be highly reactive, leading to several identified reaction products, which presumably result from hydrogen atom abstraction via the trityl C atom, e.g., from the solvent. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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13 pages, 2646 KiB  
Article
Naphthalimide-Modified Tridentate Platinum(II) Complexes: Synthesis, Characterization, and Application in Singlet Oxygen Generation
by Zhong-Liang Gong, Qing-Jun Pan, Dian-Xue Ma and Yu-Wu Zhong
Inorganics 2023, 11(11), 438; https://doi.org/10.3390/inorganics11110438 - 17 Nov 2023
Cited by 3 | Viewed by 2061
Abstract
Singlet oxygen (1O2), representing an important reactive oxygen species, has promising applications in biomedical, material, and environmental sciences. Photosensitized production of 1O2 using organic dyes is highly desirable and the exploration of highly efficient photosensitizers has received [...] Read more.
Singlet oxygen (1O2), representing an important reactive oxygen species, has promising applications in biomedical, material, and environmental sciences. Photosensitized production of 1O2 using organic dyes is highly desirable and the exploration of highly efficient photosensitizers has received considerable attention. Herein, two tridentate Pt(II) complexes, i.e., cationic 1(PF6) and neutral 2, modified with the ethynylnaphthalimide chromophore, were designed and prepared for the application in 1O2 generation. Spectroscopic studies and computational results suggest that 1(PF6) and 2 display the lowest-energy absorption bands centered at 435–465 nm with the molar extinction coefficients of 0.6–3.2 × 104 M−1 cm−1, originating from the singlet ligand-to-ligand charge transfer (1LLCT) and a mixture of 1LLCT and singlet ligand-centered (LC) transitions, respectively. Moreover, they show similar phosphorescence at 620–640 nm assigned to the Pt-perturbed triplet LC emission of the ethynylnaphthalimide moiety. Thanks to the relatively long phosphorescence lifetimes, these complexes exhibit O2-dependent phosphorescence intensities with good reversibility and stability. They are able to behave as efficient triplet photosensitizers to promote the 1O2 generation with high quantum yields (84–89%). This work indicates that the combination of an organic chromophore with Pt(II) complexes provides an effective method to obtain photosensitizers for 1O2 generation. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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11 pages, 1974 KiB  
Article
Ammonium and Phosphonium Salts Containing Monoanionic Iron(II) Half-Sandwich Complexes [Fe(η5-Cp*)X2]− (X = Cl − I)
by Julian Zinke, Clemens Bruhn and Ulrich Siemeling
Inorganics 2023, 11(11), 437; https://doi.org/10.3390/inorganics11110437 - 17 Nov 2023
Cited by 1 | Viewed by 1725
Abstract
Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2 [...] Read more.
Half-sandwich iron(II) dihalido complexes of the type [Fe(η5-Cp’)X2]− (Cp’ = C5H5 or substituted cyclopentadienyl) which are thermally stable at room temperature are extremely scarce, being limited to congeners containing the bulky C5H2-1,2,4-tBu3 ligand. We extended this to homologues [Fe(η5-Cp*)X2]− (X = Cl, Br, I) containing the particularly popular C5Me5 (Cp*) ligand. Corresponding ionic compounds ER4[Fe(η5-Cp*)X2] are easily accessible from FeX2, MCp* (M = Li, K) and a suitable halide source R4EX (E = N, P) in THF. Despite their high sensitivity towards air and moisture, the new compounds NnPr4[Fe(η5-Cp*)X2] (X = Cl, Br), NnPr4[Fe(η5-Cp*)BrCl], and PPh4[Fe(η5-Cp*)X2] (X = Cl, Br, I) were structurally characterised using single-crystal X-ray diffraction. NnPr4[Fe(η5-Cp*)Cl2] reacts readily with CO to afford [Fe(η5-Cp*)Cl(CO)2], indicating the synthetic potential of ER4[Fe(η5-Cp*)X2] in FeCp* half-sandwich chemistry. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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15 pages, 2293 KiB  
Article
Luminescent Diimine-Pt(IV) Complexes with Axial Phenyl Selenide Ligands
by Marzieh Dadkhah Aseman, Reza Babadi Aghakhanpour, Zohreh Sharifioliaei, Axel Klein and S. Masoud Nabavizadeh
Inorganics 2023, 11(10), 387; https://doi.org/10.3390/inorganics11100387 - 28 Sep 2023
Cited by 1 | Viewed by 1583
Abstract
Luminescent diimine-Pt(IV) complexes [Pt(N^N)(Me)2(PhSe)2], (N^N = 2,2′-bipyridine (bpy, 1b), 1,10-phenanthroline (phen, 2b), and 4,4′-dimethyl-2,2′-bipyridine (Me2bpy, 3b), PhSe− = phenyl selenide were prepared and identified using multinuclear (1H, 13C{1H} [...] Read more.
Luminescent diimine-Pt(IV) complexes [Pt(N^N)(Me)2(PhSe)2], (N^N = 2,2′-bipyridine (bpy, 1b), 1,10-phenanthroline (phen, 2b), and 4,4′-dimethyl-2,2′-bipyridine (Me2bpy, 3b), PhSe− = phenyl selenide were prepared and identified using multinuclear (1H, 13C{1H} and 77Se{1H}) NMR spectroscopy. The PhSe− ligands were introduced through oxidative addition of diphenyl diselenide to the non-luminescent Pt(II) precursors [Pt(N^N)(Me)2], N^N = (bpy, 1a), (phen, 2a), (Me2bpy, 3a), to give the luminescent Pt(IV) complexes 1b–3b. The UV-vis absorption spectra of 1b–3b are characterised by intense bands in the range 240–330 nm. We assigned them to transitions of essentially π−π* character with small metal and PhSe− ligand contributions with the help of TD-DFT (time-dependent density functional theory) calculations. The weak long-wavelength bands in the range 350–475 nm are of mixed ligand-to-metal charge transfer (L’MCT) (n(Se)→d(Pt)/intra-ligand charge transfer (IL’CT) (n(Se)→π*(Ph) or π(Ph)→π*(Ph))/ligand-to-ligand’ charge transfer (LL’CT) (L = N^N, L’ = PhSe−, M = Pt and n = lone pair) character. The Pt(IV) complexes showed broad emission bands in the solid state at 298 and 77 K, peaking at 560–595 nm with a blue shift upon cooling. Structured emission bands were obtained in the range 450–600 nm, with the maxima depending on the N^N ligands and the solvent polarity (CH2Cl2 vs. dimethyl sulfoxide (DMSO) and aqueous tris(hydroxymethyl)aminomethane hydrochloride (tris-HCl) buffer). The emissions originate from essentially ligand-centred triplet states (3LC) with mixed IL’CT/L’MCT contributions as concluded from the DFT calculation. Such dominating PhSe contributions to the emissive states are unprecedented in the world of luminescent diimine-Pt(IV) complexes. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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15 pages, 2711 KiB  
Article
Mono-Alkyl-Substituted Phosphinoboranes (HRP–BH2–NMe3) as Precursors for Poly(alkylphosphinoborane)s: Improved Synthesis and Comparative Study
by Felix Lehnfeld, Tim Oswald, Rüdiger Beckhaus and Manfred Scheer
Inorganics 2023, 11(10), 377; https://doi.org/10.3390/inorganics11100377 - 23 Sep 2023
Cited by 1 | Viewed by 1806
Abstract
A new synthetic pathway to various mono-alkyl-substituted phosphinoboranes HRP–BH2–NMe3 has been developed. The new synthetic route starting from alkyl halides and NaPH2 followed by metalation and salt metathesis is performed in a one-pot procedure and leads to higher yields [...] Read more.
A new synthetic pathway to various mono-alkyl-substituted phosphinoboranes HRP–BH2–NMe3 has been developed. The new synthetic route starting from alkyl halides and NaPH2 followed by metalation and salt metathesis is performed in a one-pot procedure and leads to higher yields and purity of the resulting phosphinoboranes, as compared to previously reported routes. Additionally, the scope of accessible compounds could be expanded from short-chained linear alkyl substituents to longer-chained linear alkyl substituents as well as secondary or functionalized alkyl substituents. The reported examples include primary alkyl-substituted phosphinoboranes RHP-BH2-NMe3 (R = n-butyl, n-pentyl, n-hexyl; 1a–c), the secondary alkyl-substituted derivatives iPrPH-BH2-NMe3 (2), and the functionalized alkyl-substituted 4-bromo-butyl-phosphinoborane (BrC4H8)PH-BH2-NMe3 (3). Compounds 1a, 1c, and 2 were additionally used for preliminary polymerization reactions via a thermal and a transition metal-catalyzed pathway, revealing the formation of high-molecular-weight polymers under certain conditions. Detailed investigations on the influence of temperature, concentration, substituents and reaction time on the respective polymerization reactions were performed. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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14 pages, 2913 KiB  
Article
Manganese(I) Diamine Electrocatalysts: Electrochemical Carbon Dioxide Reduction to Carbon Monoxide
by Badrinath Dhakal, Brooke A. Corbin, Alberto Sosa Parada, Jonathan G. Sakai, Emily A. Felton, Lauren T. McDonald, Anthony J. Gross, Gary S. Nichol and Greg A. N. Felton
Inorganics 2023, 11(9), 374; https://doi.org/10.3390/inorganics11090374 - 21 Sep 2023
Cited by 3 | Viewed by 3018
Abstract
Novel organometallic complexes Mn(benzene-1,2-diamine)(CO)3Br, Mn-1, Mn(3-methylbenzene-1,2-diamine)(CO)3Br, Mn-2, and Re(benzene-1,2-diamine)(CO)3Cl, Re-1, have been synthesized and characterized by IR, UV/Vis, 1H-NMR, EA and HRMS. The structures of Mn-2 and Re-1 were confirmed by X-ray crystallography. [...] Read more.
Novel organometallic complexes Mn(benzene-1,2-diamine)(CO)3Br, Mn-1, Mn(3-methylbenzene-1,2-diamine)(CO)3Br, Mn-2, and Re(benzene-1,2-diamine)(CO)3Cl, Re-1, have been synthesized and characterized by IR, UV/Vis, 1H-NMR, EA and HRMS. The structures of Mn-2 and Re-1 were confirmed by X-ray crystallography. The three novel compounds were studied for their electrocatalytic reduction of carbon dioxide to carbon monoxide using cyclic voltammetry in acetonitrile solutions. Controlled potential electrolysis was used to obtain information on faradaic yield, with product formation being confirmed by GC. Using earth-abundant manganese, compounds Mn-1 and Mn-2 display turnover frequencies of 108 s−1 and 82 s−1, respectively, amid selective production of carbon monoxide (faradaic yields ~85%), with minimal co-production of dihydrogen (<2%), and low overpotential of 0.18 V. The rhenium congener, Re-1, displays no activity as an electrocatalyst for carbon dioxide reduction under identical conditions. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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Review

Jump to: Research

21 pages, 3836 KiB  
Review
Progress on Noble-Metal-Free Organic–Inorganic Hybrids for Electrochemical Water Oxidation
by Zheng Tan, Lihua Zhang, Tong Wu, Yinbo Zhan, Bowei Zhou, Yilin Dong and Xia Long
Inorganics 2023, 11(11), 424; https://doi.org/10.3390/inorganics11110424 - 26 Oct 2023
Cited by 3 | Viewed by 2033
Abstract
Emerging as a new class of advanced functional materials with hierarchical architectures and redox characters, organic–inorganic hybrid materials (OIHs) have been well developed and widely applied in various energy conversion reactions recently. In this review, we focus on the applications and structure–performance relationship [...] Read more.
Emerging as a new class of advanced functional materials with hierarchical architectures and redox characters, organic–inorganic hybrid materials (OIHs) have been well developed and widely applied in various energy conversion reactions recently. In this review, we focus on the applications and structure–performance relationship of OIHs for electrochemical water oxidation. The general principles of water oxidation will be presented first, followed by the progresses on the applications of OIHs that are classified as metal organic frameworks (MOFs) and their derivates, covalent organic framework (COF)-based hybrids and other OIHs. The roles of organic counterparts on catalytic active centers will be fully discussed and highlighted with typical examples. Finally, the challenges and perspectives assessing this promising hybrid material as an electrocatalyst will be provided. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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20 pages, 2848 KiB  
Review
Carbon Quantum Dots: The Role of Surface Functional Groups and Proposed Mechanisms for Metal Ion Sensing
by Hasan Shabbir, Edit Csapó and Marek Wojnicki
Inorganics 2023, 11(6), 262; https://doi.org/10.3390/inorganics11060262 - 20 Jun 2023
Cited by 69 | Viewed by 9393
Abstract
Carbon dots (CDs) are zero-dimensional nanomaterials composed of carbon and surface groups attached to their surface. CDs have a size smaller than 10 nm and have potential applications in different fields such as metal ion detection, photodegradation of pollutants, and bio-imaging, in this [...] Read more.
Carbon dots (CDs) are zero-dimensional nanomaterials composed of carbon and surface groups attached to their surface. CDs have a size smaller than 10 nm and have potential applications in different fields such as metal ion detection, photodegradation of pollutants, and bio-imaging, in this review, the capabilities of CDs in metal ion detection will be described. Quantum confinement is generally viewed as the key factor contributing to the uniqueness of CDs characteristics due to their small size and the lack of attention on the surface functional groups and their roles is given, however, in this review paper, the focus will be on the functional group and the composition of CDs. The surface functional groups depend on two parameters: (i) the oxidation of precursors and (ii) their composition. The mechanism of metal ion detection is still being studied and is not fully understood. This review article emphasizes the current development and progress of CDs, focusing on metal ion detection based on a new perspective. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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