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Inorganics, Volume 9, Issue 3 (March 2021) – 3 articles

Cover Story (view full-size image): Organotin derivatives resulting from the insertion of carbon dioxide into Sn-X bonds (X = N, H, P) have been reviewed from a structural point of view. Notably, the synthetic aspects and X-ray structures of carbamato, formato and phosphinoformato tin complexes are successively described and discussed. In addition, the last chapter is devoted to bimetallic transition-metal/tin complexes with bridging carbon dioxide, also named metallocarboxylato tin complexes. Completing a previous review dedicated to hemicarbonato and carbonato derivatives, this new inventory continues to show that CO2 derivatives of molecular tin compounds can truly be considered as a class of compounds in their own right. View this paper.
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Open AccessArticle
Photoluminescent Coordination Polymers Based on Group 12 Metals and 1H-Indazole-6-Carboxylic Acid
Inorganics 2021, 9(3), 20; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9030020 - 22 Mar 2021
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Abstract
Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully [...] Read more.
Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds. Full article
(This article belongs to the Special Issue Functional Coordination Polymers and Metal–Organic Frameworks)
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Open AccessArticle
Synthesis and Characterization of NaCd0.92Sn1.08, Na(Cd0.28Sn0.72)2 and Na2CdSn5 with Three-Dimensional Cd-Sn Frameworks
Inorganics 2021, 9(3), 19; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9030019 - 06 Mar 2021
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Abstract
The crystal structures of three new ternary compounds, NaCd0.92Sn1.08 (I), Na(Cd0.28Sn0.72)2 (II), and Na2CdSn5 (III) synthesized in a sodium-cadmium-tin system were determined by single-crystal X-ray analysis to be the following: (I) LiGeZn-type [...] Read more.
The crystal structures of three new ternary compounds, NaCd0.92Sn1.08 (I), Na(Cd0.28Sn0.72)2 (II), and Na2CdSn5 (III) synthesized in a sodium-cadmium-tin system were determined by single-crystal X-ray analysis to be the following: (I) LiGeZn-type structure (hexagonal, a = 4.9326(1) Å, c = 10.8508(3) Å, space group P-6m2); (II) CaIn2-type structure (hexagonal, a = 4.8458(2) Å, c = 7.7569(3) Å, P63/mmc); and (III) isotype with tI-Na2ZnSn5 (tetragonal, a = 6.4248(1) Å, c = 22.7993(5) Å, I-42d). Each compound has a three-dimensional framework structure mainly composed of four-fold coordinated Cd and Sn atoms with Na atoms located in the framework space. Elucidation of the electrical properties of the polycrystalline samples indicated that compounds (I) and (II) are polar intermetallics with metallic conductivity, and compound (III) is a semiconducting Zintl compound. These properties were consistent with the electronic structures calculated using the ordered structure models of the compounds. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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Open AccessReview
CO2 Derivatives of Molecular Tin Compounds. Part 2: Carbamato, Formato, Phosphinoformato and Metallocarboxylato Complexes
Inorganics 2021, 9(3), 18; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9030018 - 24 Feb 2021
Viewed by 390
Abstract
Single-crystal X-ray diffraction structures of organotin compounds bearing hemicarbonate and carbonate ligands were recently reviewed by us—“CO2 Derivatives of Molecular Tin Compounds. Part 1: Hemicarbonato and Carbonato Complexes”, Inorganics 2020, 8, 31—based on crystallographic data available from the Cambridge Structural [...] Read more.
Single-crystal X-ray diffraction structures of organotin compounds bearing hemicarbonate and carbonate ligands were recently reviewed by us—“CO2 Derivatives of Molecular Tin Compounds. Part 1: Hemicarbonato and Carbonato Complexes”, Inorganics 2020, 8, 31—based on crystallographic data available from the Cambridge Structural Database. Interestingly, this first collection revealed that most of the compounds listed were isolated in the context of studies devoted to the reactivity of tin precursors towards carbon dioxide, at atmospheric pressure or under pressure, thus highlighting the suitable disposition of Sn to fix CO2. In the frame of a second part, the present review carries on to explore CO2 derivatives of molecular tin compounds by describing successively the complexes with carbamato, formato, and phosphinoformato ligands, and obtained from insertion reactions of carbon dioxide into Sn–X bonds (X = N, H, P, respectively). The last chapter is devoted to X-ray structures of transition metal/tin CO2 complexes exhibiting metallocarboxylato ligands. As in Part 1, for each tin compound reported and when described in the original study, the structural descriptions are supplemented by synthetic conditions and spectroscopic data. Full article
(This article belongs to the Special Issue Hypercoordinated Organotin Compounds)
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