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Inorganics, Volume 6, Issue 3 (September 2018)

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Open AccessReview Self-Assembly in Polyoxometalate and Metal Coordination-Based Systems: Synthetic Approaches and Developments
Inorganics 2018, 6(3), 71; https://doi.org/10.3390/inorganics6030071 (registering DOI)
Received: 8 June 2018 / Revised: 6 July 2018 / Accepted: 9 July 2018 / Published: 13 July 2018
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Abstract
Utilizing new experimental approaches and gradual understanding of the underlying chemical processes has led to advances in the self-assembly of inorganic and metal–organic compounds at a very fast pace over the last decades. Exploitation of unveiled information originating from initial experimental observations has
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Utilizing new experimental approaches and gradual understanding of the underlying chemical processes has led to advances in the self-assembly of inorganic and metal–organic compounds at a very fast pace over the last decades. Exploitation of unveiled information originating from initial experimental observations has sparked the development of new families of compounds with unique structural characteristics and functionalities. The main source of inspiration for numerous research groups originated from the implementation of the design element along with the discovery of new chemical components which can self-assemble into complex structures with wide range of sizes, topologies and functionalities. Not only do self-assembled inorganic and metal–organic chemical systems belong to families of compounds with configurable structures, but also have a vast array of physical properties which reflect the chemical information stored in the various “modular” molecular subunits. The purpose of this short review article is not the exhaustive discussion of the broad field of inorganic and metal–organic chemical systems, but the discussion of some representative examples from each category which demonstrate the implementation of new synthetic approaches and design principles. Full article
(This article belongs to the Special Issue Self-Assembly of Supramolecular Coordination Compounds)
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Open AccessArticle Chiral Tectonics: VCD and ECD Application for Epimerization of a Star-Burst Tetranuclear Complex with a Labile Central Core
Received: 21 June 2018 / Revised: 30 June 2018 / Accepted: 9 July 2018 / Published: 12 July 2018
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Abstract
The present article reports the application of vibrational circular dichroism (VCD) and temperature-dependent electronic circular dichroism (ECD) methods to reveal the dynamical aspects of a star-burst tetranuclear metal complex with a labile central core in a solution. One-handed chiral inert tecton, ∆- or
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The present article reports the application of vibrational circular dichroism (VCD) and temperature-dependent electronic circular dichroism (ECD) methods to reveal the dynamical aspects of a star-burst tetranuclear metal complex with a labile central core in a solution. One-handed chiral inert tecton, ∆- or Λ-[Ru(III)(acac)2(taetH)] (acacH = acetylacetone, taetH2 = tetraacetylethane), was prepared by reacting [Ru(acac)3] with taetH2 in solid at 120 °C. The ∆Λ-pair of pure enantiomers was obtained chromatographically. On adding Al(ClO4)3 to its enantiopure solution, three units of one-handed tecton were assembled spontaneously around an aluminum(III) ion to form a star-burst tetranuclear complex, [{∆- or Λ-Ru(acac)2(taet)}3Al(III)]. The VCD spectrum recorded on the CDCl3 solution of the complex showed that the central chirality around an Al(III) ion took dominantly the absolute configuration antipodal to those of peripheral Ru(III) units at the temperature lower than −10 °C. The complex underwent interconversion between the ∆- and Λ-configurations around a central Al(III) core (or epimerization) in solution. The activation energy barrier was determined from the time courses of ECD spectra in CHCl3 and CH3OH. Full article
(This article belongs to the Special Issue Chiral Metal Complexes)
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Open AccessArticle One-Pot Synthesis of Heavier Group 14 N-Heterocyclic Carbene Using Organosilicon Reductant
Received: 6 June 2018 / Revised: 25 June 2018 / Accepted: 30 June 2018 / Published: 12 July 2018
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Abstract
Syntheses of heavier Group 14 analogues of “Arduengo-type” N-heterocyclic carbene majorly involved the use of conventional alkali metal-based reducing agents under harsh reaction conditions. The accompanied reductant-derived metal salts and chances of over-reduced impurities often led to isolation difficulties in this multi-step
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Syntheses of heavier Group 14 analogues of “Arduengo-type” N-heterocyclic carbene majorly involved the use of conventional alkali metal-based reducing agents under harsh reaction conditions. The accompanied reductant-derived metal salts and chances of over-reduced impurities often led to isolation difficulties in this multi-step process. In order to overcome these shortcomings, we have used 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene as a milder reducing agent for the preparation of N-heterocyclic germylenes (NHGe) and stannylenes (NHSn). The reaction occurs in a single step with moderate yields from the mixture of N-substituted 1,4-diaza-1,3-butadiene, E(II) (E(II) = GeCl2·dioxane, SnCl2) and the organosilicon reductant. The volatile byproducts trimethylsilyl chloride and pyrazine could be removed readily under vacuum. No significant over reduction was observed in this process. However, N-heterocyclic silylene (NHSi) could not be synthesized using an even stronger organosilicon reductant under thermal and photochemical conditions. Full article
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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Open AccessArticle Synthesis of Ferrocenyl-Substituted Organochalcogenyldichlorogermanes
Received: 13 June 2018 / Revised: 6 July 2018 / Accepted: 9 July 2018 / Published: 11 July 2018
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Abstract
Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2 (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed
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Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2 (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed isolating stable crystalline organochalcogenyldichlorogermanes. Full article
(This article belongs to the Special Issue Metallocene Complexes)
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Open AccessArticle Metallated [3]Ferrocenophanes Containing P3M Bridges (M = Li, Na, K) §
Received: 19 June 2018 / Revised: 4 July 2018 / Accepted: 6 July 2018 / Published: 11 July 2018
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Abstract
Alkali-metal phosphanides can be embedded into a [3]ferrocenophane scaffold giving rise to bicyclic ferrocenophanes [MFe(C5H4PtBu)2P] (M = Li, Na, K). Coordination of the alkali-metal ions takes place via the terminal phosphorus atoms adopting a puckered
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Alkali-metal phosphanides can be embedded into a [3]ferrocenophane scaffold giving rise to bicyclic ferrocenophanes [MFe(C5H4PtBu)2P] (M = Li, Na, K). Coordination of the alkali-metal ions takes place via the terminal phosphorus atoms adopting a puckered P3M four-membered ring. All compounds were characterized via single-crystal X-ray diffraction and multinuclear NMR spectroscopy (1H, 31P, 7Li), whereas 13C NMR data could only be recorded for the Li derivative, owing to the limited solubility of its heavier congeners in unreactive solvents. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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Open AccessCommunication Synthesis, Structural, and Magnetic Characterization of a Mixed 3d/4f 12-Metallacrown-4 Family of Complexes
Received: 21 June 2018 / Revised: 2 July 2018 / Accepted: 5 July 2018 / Published: 7 July 2018
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Abstract
A new family of complexes (tBu4N){[LnIII(O2CBut)4][12-MC-Mn(III)N(shi)-4]}·5CH2Cl2 (Ln = Gd (1) and Tb (2)), (tBu4N)2{[YIII(O
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A new family of complexes (tBu4N){[LnIII(O2CBut)4][12-MC-Mn(III)N(shi)-4]}·5CH2Cl2 (Ln = Gd (1) and Tb (2)), (tBu4N)2{[YIII(O2CBut)4][12-MC-Mn(III)N(shi)-4]}(ClO4) (3); where shiH3 = salicylhydroxamic acid; ButCO2 = pivalate ions; tBu4N = tetrabutylammonium and ClO4 = perchlorate ions, has been isolated. The reaction of salicylhydroxamic acid with Mn(O2CBut)2·2H2O, Ln(NO3)3·xH2O, tBu4NClO4 in the presence of morpholine (C4H9NO) led to the isolation of compounds 13. The complexes belong to the 12-MC-4 family of Metallacrowns (MCs) possessing a central {Mn4IIILnIII(µ-NO)4}11+ core with the four MnIII atoms occupying the periphery positions, while the formed [Mn–N–O] repeating unit, assists in the accommodation of the LnIII atom in the center of the ring. Peripheral ligation is provided by four η11:μ pivalate ions. Direct current magnetic susceptibility (dc) measurements revealed the presence of predominant antiferromagnetic exchange interactions within the metal centers. A 1-J fitting model was used in order to quantify the MnIII–MnIII interactions and fitting of the data, for the diamagnetic YIII analogue, gave J = −3.74 cm−1 and gMn(III) = 2.07. Fitting of the {Mn4Gd} compound using a 2-J model, counting additionally for the MnIII–GdIII interactions, revealed values of J1 = −3.52 cm−1, J2 = −0.45 cm−1, and gMn(III) = 1.99. Full article
(This article belongs to the Special Issue Organometallic Macrocycles and Their Applications)
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Open AccessReview Group 4 Metallocene Polymers—Selected Properties and Applications
Received: 27 May 2018 / Revised: 16 June 2018 / Accepted: 20 June 2018 / Published: 26 June 2018
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Abstract
Group 4 metallocene polymers offer a wide variety of unique properties. Some of these are reviewed in this paper, including the ability to form fibers and to absorb laser radiation, thereby protecting materials containing them in small amounts; the possibility of becoming conductive
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Group 4 metallocene polymers offer a wide variety of unique properties. Some of these are reviewed in this paper, including the ability to form fibers and to absorb laser radiation, thereby protecting materials containing them in small amounts; the possibility of becoming conductive materials through simple doping; increasing the productivity of damaged, old and mold-infested seeds through incorporation of plant growth hormones; and acting as anticancer drugs that inhibit a variety of human cancers including breast and pancreatic cancers. Full article
(This article belongs to the Special Issue Metallocene Complexes)
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Open AccessArticle Regium-π vs Cation-π Interactions in M2 and MCl (M = Cu, Ag and Au) Complexes with Small Aromatic Systems: An ab Initio Study
Received: 5 June 2018 / Revised: 18 June 2018 / Accepted: 21 June 2018 / Published: 24 June 2018
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Abstract
In this study we have theoretically analyzed (RI-MP2/def2-TZVP) the ability of metal moieties involving elements from group IB (Cu, Ag and Au) to establish either regium-π or cation-π interactions with π-systems of different electronic nature. More precisely, we have used M2 (oxidation
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In this study we have theoretically analyzed (RI-MP2/def2-TZVP) the ability of metal moieties involving elements from group IB (Cu, Ag and Au) to establish either regium-π or cation-π interactions with π-systems of different electronic nature. More precisely, we have used M2 (oxidation state = 0) and MCl (oxidation state = +1) molecules where M = Cu, Ag and Au. On the other hand, we have used benzene, trifluorobenzene and hexafluorobenzene as aromatic rings. Furthermore, we have used Bader’s theory of “Atoms in Molecules” as well as NBO (Natural Bonding Orbital) calculations to further investigate and characterize the regium-π and cation-π complexes described herein. We believe our findings may be important when describing and characterizing both interactions in a chemical context, as well as to further explore the nature of the recently uncovered regium-π bond. Full article
(This article belongs to the Special Issue Novel Non-Covalent Interactions)
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