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Inorganics, Volume 7, Issue 10 (October 2019)

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Cover Story (view full-size image) Defective Zr- based metal–organic framework UiO-66 was prepared by adding a large amount of formic [...] Read more.
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Open AccessArticle
Heterobimetallic Chromium Manganese Carbonyl Nitrosyls: Comparison with Isoelectronic Homometallic Binuclear Chromium Carbonyl Nitrosyls and Manganese Carbonyls
Inorganics 2019, 7(10), 127; https://doi.org/10.3390/inorganics7100127 - 21 Oct 2019
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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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An Optical Power Limiting and Ultrafast Photophysics Investigation of a Series of Multi-Branched Heavy Atom Substituted Fluorene Molecules
Inorganics 2019, 7(10), 126; https://doi.org/10.3390/inorganics7100126 - 18 Oct 2019
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A common molecular design paradigm for optical power limiting (OPL) applications is to introduce heavy atoms that promote intersystem crossing and triplet excited states. In order to investigate this effect, three multi-branched fluorene molecules were prepared where the central moiety was either an [...] Read more.
A common molecular design paradigm for optical power limiting (OPL) applications is to introduce heavy atoms that promote intersystem crossing and triplet excited states. In order to investigate this effect, three multi-branched fluorene molecules were prepared where the central moiety was either an organic benzene unit, para-dibromobenzene, or a platinum(II)–alkynyl unit. All three molecules showed good nanosecond OPL performance in solution. However, only the dibromobenzene and Pt–alkynyl compounds showed strong microsecond triplet excited state absorption (ESA). To investigate the photophysical cause of the OPL, especially for the fully organic molecule, photokinetic measurements including ultrafast pump–probe spectroscopy were performed. At nanosecond timescales, the ESA of the organic molecule was larger than the two with intersystem crossing (ISC) promoters, explaining its good OPL performance. This points to a design strategy where the singlet-state ESA is balanced with the ISC rate to increase OPL performance at the beginning of a nanosecond pulse. Full article
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Open AccessCommunication
Synthesis of a Half-Sandwich Hydroxidoiridium(III) Complex Bearing a Nonprotic N-Sulfonyldiamine Ligand and Its Transformations Triggered by the Brønsted Basicity
Inorganics 2019, 7(10), 125; https://doi.org/10.3390/inorganics7100125 - 17 Oct 2019
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Synthesis and reactivities of a new mononuclear hydroxidoiridium(III) complex with a pentamethylcyclopentadienyl (Cp*) ligand are reported. The hydroxido ligand was introduced into an iridium complex having a nonprotic amine chelate derived from N-mesyl-N’,N’-dimethylethylenediamine by substitution of the chloride [...] Read more.
Synthesis and reactivities of a new mononuclear hydroxidoiridium(III) complex with a pentamethylcyclopentadienyl (Cp*) ligand are reported. The hydroxido ligand was introduced into an iridium complex having a nonprotic amine chelate derived from N-mesyl-N’,N’-dimethylethylenediamine by substitution of the chloride ligand using KOH. The resulting hydroxidoiridium complex was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The hydroxido complex was able to deprotonate benzamide and acetonitrile, and showed an ability to accept a hydride from 2-propanol to generate the corresponding hydrido complex quantitatively. In the reaction with mandelonitrile, a cyanide anion was transferred to the iridium center in preference to the hydride transfer. The cyanidoiridium complex was also identified in the reaction with acetone cyanohydrin, and could serve as catalyst species in the transfer hydrocyanation of benzaldehyde. Full article
(This article belongs to the Special Issue Iridium Complexes)
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Open AccessReview
Highlights on Gold TADF Complexes
Inorganics 2019, 7(10), 124; https://doi.org/10.3390/inorganics7100124 - 11 Oct 2019
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Abstract
Thermally activated delayed fluorescence (TADF) and TADF-organic light-emitting diodes (OLEDs) systems are being given increasing attention in research nowadays. Much more work has been done for organic-based materials in this field, but the use of TADF organometallic systems has also emerged in recent [...] Read more.
Thermally activated delayed fluorescence (TADF) and TADF-organic light-emitting diodes (OLEDs) systems are being given increasing attention in research nowadays. Much more work has been done for organic-based materials in this field, but the use of TADF organometallic systems has also emerged in recent years. In particular, TADF-based gold compounds have not been particularly well-explored, with a higher number of examples of Au(I)-molecules and fewer for the higher oxidation state Au(III) derivatives. Nevertheless, the novelty and observed results deserve attention. A careful analysis has been performed in this review by classifying the reported compounds into two different groups regarding the oxidation state of the metal, and within each group, the ancillary ligands. Specific examples to illustrate their potential applications are included in the different sections. Full article
(This article belongs to the Special Issue Gold Complexes)
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Open AccessArticle
Post Synthetic Defect Engineering of UiO-66 Metal–Organic Framework with An Iridium(III)-HEDTA Complex and Application in Water Oxidation Catalysis
Inorganics 2019, 7(10), 123; https://doi.org/10.3390/inorganics7100123 - 10 Oct 2019
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Clean production of renewable fuels is a great challenge of our scientific community. Iridium complexes have demonstrated a superior catalytic activity in the water oxidation (WO) reaction, which is a crucial step in water splitting process. Herein, we have used a defective zirconium [...] Read more.
Clean production of renewable fuels is a great challenge of our scientific community. Iridium complexes have demonstrated a superior catalytic activity in the water oxidation (WO) reaction, which is a crucial step in water splitting process. Herein, we have used a defective zirconium metal–organic framework (MOF) with UiO-66 structure as support of a highly active Ir complex based on EDTA with the formula [Ir(HEDTA)Cl]Na. The defects are induced by the partial substitution of terephthalic acid with smaller formate groups. Anchoring of the complex occurs through a post-synthetic exchange of formate anions, coordinated at the zirconium clusters of the MOF, with the free carboxylate group of the [Ir(HEDTA)Cl] complex. The modified material was tested as a heterogeneous catalyst for the WO reaction by using cerium ammonium nitrate (CAN) as the sacrificial agent. Although turnover frequency (TOF) and turnover number (TON) values are comparable to those of other iridium heterogenized catalysts, the MOF exhibits iridium leaching not limited at the first catalytic run, as usually observed, suggesting a lack of stability of the hybrid system under strong oxidative conditions. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
Arsenates of Divalent Metals Comprising Arsenic Acid—An Update
Inorganics 2019, 7(10), 122; https://doi.org/10.3390/inorganics7100122 - 09 Oct 2019
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Abstract
Divalent metal oxidoarsenates(V) with compositions M(H2AsO4)2(H3AsO4)2 (M = Mg, Mn, Co, Ni), M(HAsO4)(H3AsO4)(H2O)0.5 (M = Mn, Cd) and Zn(HAsO [...] Read more.
Divalent metal oxidoarsenates(V) with compositions M(H2AsO4)2(H3AsO4)2 (M = Mg, Mn, Co, Ni), M(HAsO4)(H3AsO4)(H2O)0.5 (M = Mn, Cd) and Zn(HAsO4)(H3AsO4) were obtained from solutions containing an excess of arsenic acid. Single crystal X-ray diffraction revealed isotypism of the M(H2AsO4)2(H3AsO4)2 (M = Mg, Mn, Co, Ni) structures with the known Cu and Zn members of this series whereas M(HAsO4)(H3AsO4)(H2O)0.5 (M = Mn, Cd) and Zn(HAsO4)(H3AsO4) crystallize in novel structure types. The two isotypic M(HAsO4)(H3AsO4)(H2O)0.5 (M = Mn, Cd) structures are closely related with that of Zn(HAsO4)(H3AsO4). Both comprise undulating centrosymmetric [ 1 MO4/2O2/1] chains that share corners with HAsO42 tetrahedra and H3AsO4 tetrahedra to build up layers extending along (001). Intermediate water molecules (occupancy 0.5) link adjacent layers in the water-containing compound whereas the linkage in the Zn-compound is mediated by weak hydrogen bonding interactions between the layers. Results of a quantitative comparison between all known structures of the M(H2XO4)2(H3XO4)2 (M = Mg, Mn, Co, Ni, Cu, Zn; X = P, As) series as well as between the two M(HAsO4)(H3AsO4)(H2O)0.5 (M = Mn, Cd) structures are presented. Full article
(This article belongs to the Special Issue Oxido Compounds)
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Open AccessArticle
Successive Activation of C–H and C–O Bonds of Vinyl Ethers by a Diphosphine and Hydrido-Bridged Diiridium Complex
Inorganics 2019, 7(10), 121; https://doi.org/10.3390/inorganics7100121 - 03 Oct 2019
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Abstract
The reaction of [(Cp*Ir)2(μ-dmpm)(μ-H)][OTf] (2) [Cp* = η5-C5Me5, dmpm = bis(dimethylphosphino)methane] with 2,3-dihydrofuran gives [(Cp*IrH)2(μ-dmpm){μ-(2,3-dihydrofuranyl)}][OTf] (3) in an isolated yield of 70% via the C–H bond activation at the 5-position of 2,3-dihydrofuran. Complex [...] Read more.
The reaction of [(Cp*Ir)2(μ-dmpm)(μ-H)][OTf] (2) [Cp* = η5-C5Me5, dmpm = bis(dimethylphosphino)methane] with 2,3-dihydrofuran gives [(Cp*IrH)2(μ-dmpm){μ-(2,3-dihydrofuranyl)}][OTf] (3) in an isolated yield of 70% via the C–H bond activation at the 5-position of 2,3-dihydrofuran. Complex 3 is slowly converted into [(Cp*Ir)2(μ-dmpm)(μ-C=C(H)CH2CH2OH)][OTf] (4) quantitatively via the proton-mediated C–O bond activation. The reaction of 2 with ethyl vinyl ether gives [(Cp*Ir)2(μ-dmpm)(μ-CH=CH2)][OTf] (5) in the isolated yield of 64% via the successive activation of C–H and C–O bonds. Full article
(This article belongs to the Special Issue Iridium Complexes)
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Open AccessArticle
AgCl-ZnAl Layered Double Hydroxides as Catalysts with Enhanced Photodegradation and Antibacterial Activities
Inorganics 2019, 7(10), 120; https://doi.org/10.3390/inorganics7100120 - 03 Oct 2019
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Abstract
Surface-modified ZnAl layered double hydroxides (LDHs) were prepared by reaction of AgNO3, with both ZnAlCl (LDH1) and ZnAlCO3 exchanged on the surface with chloride anions (LDH3). In this way, AgCl nanoparticles with crystalline domains ranging from 40 to 100 nm [...] Read more.
Surface-modified ZnAl layered double hydroxides (LDHs) were prepared by reaction of AgNO3, with both ZnAlCl (LDH1) and ZnAlCO3 exchanged on the surface with chloride anions (LDH3). In this way, AgCl nanoparticles with crystalline domains ranging from 40 to 100 nm were grown on the LDH surface. An additional sample was prepared by partial reduction of silver to obtain [email protected] (LDH2). The composites were tested as catalysts in Rhodamine B (RhB) degradation, wherein LDH2 showed complete cleavage of RhB after 45 min of irradiation versus 70 min needed in the presence of AgCl. This time decreased to 35 min for LDH1 and 15 min for LDH3, underlining the role of the AgCl dimensions and anion in the interlayer region. Studies on the reactive species involved in the degradation process revealed that, for all catalysts, O2· was the main active species, while, to some extent, holes contribute to the activity of the LDH3. Finally, the composites showed high bactericidal activity, under irradiation, against Escherichia coli, comparable with that of Gentamicin, the positive control. A synergic effect of silver released from the composites and the production of reactive oxygen species was considered. Full article
(This article belongs to the Special Issue Recent Breakthroughs with Layered Double Hydroxides)
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Open AccessArticle
A Raman Spectroscopic and Computational Study of New Aromatic Pyrimidine-Based Halogen Bond Acceptors
Inorganics 2019, 7(10), 119; https://doi.org/10.3390/inorganics7100119 - 02 Oct 2019
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Abstract
Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene [...] Read more.
Two new aromatic pyrimidine-based derivatives designed specifically for halogen bond directed self-assembly are investigated through a combination of high-resolution Raman spectroscopy, X-ray crystallography, and computational quantum chemistry. The vibrational frequencies of these new molecular building blocks, pyrimidine capped with furan (PrmF) and thiophene (PrmT), are compared to those previously assigned for pyrimidine (Prm). The modifications affect only a select few of the normal modes of Prm, most noticeably its signature ring breathing mode, ν1. Structural analyses afforded by X-ray crystallography, and computed interaction energies from density functional theory computations indicate that, although weak hydrogen bonding (C–H···O or C–H···N interactions) is present in these pyrimidine-based solid-state co-crystals, halogen bonding and π-stacking interactions play more dominant roles in driving their molecular-assembly. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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Open AccessArticle
Morphology and Structural Stability of Bismuth-Gadolinium Co-Doped Ceria Electrolyte Nanopowders
Inorganics 2019, 7(10), 118; https://doi.org/10.3390/inorganics7100118 - 28 Sep 2019
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Abstract
The reduction of the sintering temperature of doped ceria ceramics remains an open challenge for their real exploitation as electrolytes for intermediate temperature solid oxide fuel cell (IT-SOFCs) at the industrial level. In this work, we have used Bi (0.5 and 2 mol [...] Read more.
The reduction of the sintering temperature of doped ceria ceramics remains an open challenge for their real exploitation as electrolytes for intermediate temperature solid oxide fuel cell (IT-SOFCs) at the industrial level. In this work, we have used Bi (0.5 and 2 mol %) as the sintering aid for Gd (20 mol %)-doped ceria. Nano-sized powders of Bi/Gd co-doped ceria were easily synthesized via a simple and cheap sol-gel combustion synthesis. The obtained powders showed high sinterability and very good electrochemical properties. More importantly, even after prolonged annealing at 700 °C, both of the powders and of the sintered pellets, no trace of structural modifications, phase instabilities, or Bi segregation appeared. Therefore, the use of a small amount of Bi can be taken into account for preparing ceria-based ceramic electrolytes at low sintering temperatures. Full article
(This article belongs to the Special Issue Rare Earth-Doped Ceria Systems and Their Applications)
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Open AccessArticle
Reduction of 2,2′-Bipyridine by Quasi-Linear 3d-Metal(I) Silylamides—A Structural and Spectroscopic Study
Inorganics 2019, 7(10), 117; https://doi.org/10.3390/inorganics7100117 - 25 Sep 2019
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Abstract
Quasi-linear anionic 3d-metal(I) silylamides are a new and promising class of molecules. Due to their highly negative reduction potential we wanted to test their capability to reduce substrates under coordination of their monoanionic radicaloid form. In a proof of principle study, we present [...] Read more.
Quasi-linear anionic 3d-metal(I) silylamides are a new and promising class of molecules. Due to their highly negative reduction potential we wanted to test their capability to reduce substrates under coordination of their monoanionic radicaloid form. In a proof of principle study, we present the results of the reaction of metal(I) silylamides of chromium to cobalt with 2,2′-bipyridine (bipy), the redox non-innocence and reducibility of which was already established. In the course of these studies complexes of the type K{18-crown-6}[M(hmds)2(bipy)] (hmds = –N(SiMe3)2) were obtained. These compounds were isolated and thoroughly characterized to confirm the electron transfer onto the bipyridine ligand, which now acts as a radical monoanion. For comparison of the structural changes of the bipyridine ligand, the analogous zinc complexes were also synthesized. Overall our results indicate that anionic metal(I) silylamides are capable of reducing and ligate substrates, even when the electrochemical reduction potential of the latter is by up to 1 V higher. Full article
(This article belongs to the Special Issue First-Row Transition Metal Complexes)
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Open AccessArticle
Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane
Inorganics 2019, 7(10), 116; https://doi.org/10.3390/inorganics7100116 - 20 Sep 2019
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Abstract
Two dinitrosyl iron and cobalt complexes [Fe(NO)2(L1”)](BF4) and [Co(NO)2(L1”)](BF4) are synthesized and characterized, supported by a less hindered bidentate nitrogen ligand bis(3,5-diisopropyl-1-pyrazolyl)methane (denoted as L1”), are surprisingly stable under argon atmosphere. X-ray structural analysis shows [...] Read more.
Two dinitrosyl iron and cobalt complexes [Fe(NO)2(L1”)](BF4) and [Co(NO)2(L1”)](BF4) are synthesized and characterized, supported by a less hindered bidentate nitrogen ligand bis(3,5-diisopropyl-1-pyrazolyl)methane (denoted as L1”), are surprisingly stable under argon atmosphere. X-ray structural analysis shows a distorted tetrahedral geometry. Spectroscopic and structural parameters of the dinitrosyl iron and cobalt complexes are consistent with the previous reported {Fe(NO)2}9 and {Co(NO)2}10. Two N–O and M–N(O) stretching frequencies and their magnetic properties are also consistent with the above electronic structural assignments. We explored the dioxygen reactivities of the obtained dinitrosyl complexes. Moreover, the related [FeCl2(L1”)], [Co(NO3)2(L1”)], and [Co(NO2)2(L1”)] complexes are also characterized in detail. Full article
(This article belongs to the Special Issue Scorpionates: Recent Advances)
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