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Inorganics, Volume 9, Issue 7 (July 2021) – 9 articles

Cover Story (view full-size image): Two Yb(hfac)3 (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate) or Dy(facam)3 (facam = 3-trifluoro-acetyl-(+)-camphorate) units have been bridged by the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad leading to the formation of the two [Yb2(hfac)6(L)]×2(C7H16) and [Dy2((+)facam)6(L)]×2(C6H14) dinuclear complexes. The dysprosium derivative displayed slow magnetic relaxation in the zero magnetic field through both Raman and Quantum Tunneling of the magnetization processes. The ytterbium derivative displayed both field-induced single-molecule magnet behavior and a metal-centered near infrared luminescence. The correlation between the magnetic and emissive properties agreed with a dominant magnetic relaxation through a Raman process. View this paper.
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Review
Molecular Bottom-Up Approaches for the Synthesis of Inorganic and Hybrid Nanostructures
Inorganics 2021, 9(7), 58; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070058 - 17 Jul 2021
Cited by 2 | Viewed by 825
Abstract
Chemical routes for the synthesis of nanostructures are fundamental in nanoscience. Among the different strategies for the production of nanostructures, this article reviews the fundamentals of the bottom-up approaches, focusing on wet chemistry synthesis. It offers a general view on the synthesis of [...] Read more.
Chemical routes for the synthesis of nanostructures are fundamental in nanoscience. Among the different strategies for the production of nanostructures, this article reviews the fundamentals of the bottom-up approaches, focusing on wet chemistry synthesis. It offers a general view on the synthesis of different inorganic and hybrid organic–inorganic nanostructures such as ceramics, metal, and semiconductor nanoparticles, mesoporous structures, and metal–organic frameworks. This review article is especially written for a wide audience demanding a text focused on the basic concepts and ideas of the synthesis of inorganic and hybrid nanostructures. It is styled for both early researchers who are starting to work on this topic and also non-specialist readers with a basic background on chemistry. Updated references and texts that provide a deeper discussion and describing the different synthesis strategies in detail are given, as well as a section on the current perspectives and possible future evolution. Full article
(This article belongs to the Special Issue Inorganic Nanostructures)
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Article
Ferrocenylmethylphosphanes and the Alpha Process for Methoxycarbonylation: The Original Story
Inorganics 2021, 9(7), 57; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070057 - 17 Jul 2021
Viewed by 861
Abstract
The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis [...] Read more.
The Lucite Alpha process is the predominant technology for the preparation of acrylics. This two-stage process involves the palladium-catalysed formation of methyl propanoate from ethene, CO, and methanol, followed by the oxidative formylation of methyl propanoate into methyl methacrylate. A range of bis-1,2-disubstituted aminomethylferrocenes has been prepared and characterised. These complexes serve as precursors to a variety of bulky ferrocenylmethyldiphosphanes that, in turn, function as ligands in the palladium-catalysed process. We describe the crystal structures of five ligand precursors and provide a rationale for their design. In situ catalyst testing on palladium complexes derived from ferrocenylphosphanes demonstrates that these are highly selective (>99.5%) catalysts for the formation of methyl propanoate from ethene, CO, and methanol and have turnover numbers exceeding 50,000. This article credits those researchers who worked on this project in the early days, who received little or no credit for their achievements and endeavours. Full article
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Review
Application of Metal Halide Perovskites as Photocatalysts in Organic Reactions
Inorganics 2021, 9(7), 56; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070056 - 13 Jul 2021
Cited by 1 | Viewed by 956
Abstract
This review summarizes the current status of the application of metal halide perovskites (MHPs) as photocatalysts in organic syntheses/transformations. It is shown that the optimal and unique electronic properties of MHPs can be advantageously used in several reaction types providing pros with respect [...] Read more.
This review summarizes the current status of the application of metal halide perovskites (MHPs) as photocatalysts in organic syntheses/transformations. It is shown that the optimal and unique electronic properties of MHPs can be advantageously used in several reaction types providing pros with respect to traditional photocatalysts. While still being at infancy, such field of application of MHPs as effective photocatalysts will for sure become a central research topic in the forthcoming years, thanks also to their rich structural and chemical tunability, which may provide tailored materials for most of the envisaged organic reactions. Full article
(This article belongs to the Special Issue Perovskite Photocatalysts)
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Review
Arene-Osmium(II) Complexes in Homogeneous Catalysis
Inorganics 2021, 9(7), 55; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070055 - 12 Jul 2021
Viewed by 750
Abstract
Although the application of arene-osmium(II) complexes in homogeneous catalysis has been much less studied than that of their ruthenium analogues, different works have shown that, in some instances, a comparable or even superior effectiveness can be achieved with this particular class of compounds. [...] Read more.
Although the application of arene-osmium(II) complexes in homogeneous catalysis has been much less studied than that of their ruthenium analogues, different works have shown that, in some instances, a comparable or even superior effectiveness can be achieved with this particular class of compounds. This review article focuses on the catalytic applications of arene-osmium(II) complexes. Among others, transfer hydrogenation, hydrogenation, oxidation, and nitrile hydration reactions, as well as different C-C bond forming processes, are comprehensively discussed. Full article
(This article belongs to the Special Issue Metal Arene Complexes)
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Article
Isomeric 4,2′:6′,4″- and 3,2′:6′,3″-Terpyridines with Isomeric 4′-Trifluoromethylphenyl Substituents: Effects on the Assembly of Coordination Polymers with [Cu(hfacac)2] (Hhfacac = Hexafluoropentane-2,4-dione)
Inorganics 2021, 9(7), 54; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070054 - 10 Jul 2021
Viewed by 704
Abstract
The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1) [...] Read more.
The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n·2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n·2nC6H5Me, [Cu2(hfacac)4(3)2]n·nC6H4Cl2, [Cu2(hfacac)4(3)2]n·nC6H5Cl, and [Cu(hfacac)2(4)]n·nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2]·H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n·2nC6H4Cl2 and [Cu(hfacac)2(2)]n·2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n·nC6H4Cl2 and [Cu(hfacac)2(4)]n·nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n·nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n·nC6H4Cl2 and [Cu(hfacac)2(4)]n·nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Article
Stereochemical Geometries and Photoluminescence in Pseudo-Halido-Zinc(II) Complexes. Structural Comparison between the Corresponding Cadmium(II) Analogs
Inorganics 2021, 9(7), 53; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070053 - 09 Jul 2021
Cited by 1 | Viewed by 673
Abstract
Six pseudohalide zinc(II) containing a variety of N-donor auxiliary amines were structurally characterized. These include two mononuclear trigonal bipyramidal [Zn(NTB)(N3)]ClO4·½H2O (3) and [Zn(TPA)(NCS)]ClO4 (4), two distorted octahedral [Zn(1,8-damnph)2(dca)2 [...] Read more.
Six pseudohalide zinc(II) containing a variety of N-donor auxiliary amines were structurally characterized. These include two mononuclear trigonal bipyramidal [Zn(NTB)(N3)]ClO4·½H2O (3) and [Zn(TPA)(NCS)]ClO4 (4), two distorted octahedral [Zn(1,8-damnph)2(dca)2] (5) and [Zn(8-amq)2(dca)2] (6a) as well as two 1D polymeric chains catena-[Zn(isq)21,5-dca)2] (7) and catena-[Zn(N,N-Me2en)21,5-dca)]dca (8), where NTB = tris(2-benzimidazolylmethyl)amine, TPA = tris(2-pyridylmethyl)amine, 1,8-damnph = 1,8-diaminonaphthalene, 8-amq = 8-amino-quinoline, isq = isoquinoline (isq) and N,N-Me2en = N,N-dimethylethylenediamine. In general, with the exception of 6 and 8, the complexes exhibited luminescence emission in MeOH associated with red shift of the emission maxima, and the strongest visible fluorescence peak was detected at 421 nm (λex = 330 nm) in the case of Complex 5. Full article
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Article
Mono- and Dinuclear Aluminium Complexes Derived from Biguanide and Carbothiamide Ligands
Inorganics 2021, 9(7), 52; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070052 - 07 Jul 2021
Viewed by 722
Abstract
Dianionic N,N-chelating ligands play a crucial role in coordination chemistry, but reports on related complexes remain limited to certain types of ligands. In here, the reactions of two diprotic ligands, i.e., a biguanide and a carbothiamide, with trimethylaluminium, are reported, which give rise [...] Read more.
Dianionic N,N-chelating ligands play a crucial role in coordination chemistry, but reports on related complexes remain limited to certain types of ligands. In here, the reactions of two diprotic ligands, i.e., a biguanide and a carbothiamide, with trimethylaluminium, are reported, which give rise to mono- and dinuclear aluminium(III) complexes. In addition, single deprotonation of the diprotic biguanide using potassium bis(trimethylsilyl)amide gives rise to a one-dimensional coordination polymer. All complexes have been fully characterized, and their solid-state structures were determined by single crystal X-ray diffraction analysis. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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Article
A Dy(III) Fluorescent Single-Molecule Magnet Based on a Rhodamine 6G Ligand
Inorganics 2021, 9(7), 51; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070051 - 29 Jun 2021
Viewed by 590
Abstract
The complexes of lanthanide metals, especially dysprosium, can generally exhibit excellent magnetic properties. By means of modifying ligands, dual functions or even multi-functions can be achieved. Here, we synthesized an eight-coordinate Dy(III) complex 1, [Dy(HL-o)2(MeOH)2](ClO4)3 [...] Read more.
The complexes of lanthanide metals, especially dysprosium, can generally exhibit excellent magnetic properties. By means of modifying ligands, dual functions or even multi-functions can be achieved. Here, we synthesized an eight-coordinate Dy(III) complex 1, [Dy(HL-o)2(MeOH)2](ClO4)3·4.5MeOH, which is single-molecule magnet (SMM), and the introduction of the rhodamine 6G chromophore in the ring-opened ligand HL-o realizes ligand-centered fluorescence in addition to SMM. Magnetic measurements and ab initio calculations indicate that the magnetic relaxation for complex 1 should be due to the Raman relaxation process. Studies on magneto-structural correlationship of the rhodamine salicylaldehyde hydrazone Dy(III) complexes show that the calculated energy of the first Kramers Doublet (EKD1) is basically related to the Ophenoxy-Dy-Ophenoxy bond angle, i.e., the larger Ophenoxy-Dy-Ophenoxy bond angle corresponds to a larger EKD1. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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Article
Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand
Inorganics 2021, 9(7), 50; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9070050 - 23 Jun 2021
Viewed by 658
Abstract
The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6 [...] Read more.
The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6(L)]·2(C7H16) ((1)·2(C7H16)) and [Dy2((+)facam)6(L)]·2(C6H14) ((2)·2(C6H14)). The X-ray structures reveal that the L triad bridges two terminal Yb(hfac)3 or Dy(facam)3 units. (1)·2(C7H16) behaved as a near infrared YbIII centered emitter and a field-induced Single-Molecule Magnet (SMM) while (2)·2(C6H14) displayed SMM behavior in both zero- and in-dc field. The magnetization mainly relaxes through a Raman process for both complexes under an optimal applied magnetic field. Full article
(This article belongs to the Special Issue Lanthanide Single-Molecule Magnets)
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