Crystalline chalcogenidometalate-based compounds from uncommon reaction media

Dehnen, Stefanie; Stuhrmann, Gina; Wu, Zhou

doi:10.1039/d2cc04061a

Cited by 7 publications

(5 citation statements)

References 135 publications

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“…Another property of imidazolium-based ionic liquids of the general type (C m (C n )C o Im)X (m, n, o = number of C atoms in the alkyl chains at positions 1, 2, and 3 of the Im ring, X = anion), which was discovered only recently, is their simultaneous function as the reaction medium and reactant during the synthesis of crystalline chalcogenido metalate clusters with organic decoration. − In this case, the ionic liquid thus acts as a “noninnocent” reaction medium at temperatures between 60 and 180 °C. This can take place in one of two different ways.…”

Section: Introductionmentioning

confidence: 99%

Ionothermal Approach to Homo- and Heteroleptic Alkylation of Tellurido Mercurate Clusters for Assembly in Lamellar Crystal Structures

Tallu,

Peters,

Friedrich

et al. 2023

Inorg. Chem.

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The selective methylation and butylation of chalcogenido metalate clusters by utilizing imidazolium-based ionic liquids turned out to be not only a comparably mild but at the same time also the only known method for postsynthetic alkylation of such species in order to increase their solubility. For additional impact on the crystal structures, selective alkylation with longer alkyl chains was addressed by utilizing the ionic liquid (C 10 C 1 Im)[BF 4 ] (C 10 = decyl group at position 1 and C 1 = methyl group at position 3 of the cation's Im = imidazolium ring) for ionothermal syntheses of functionalized tellurido mercurate clusters. Herein, we report three novel compounds, two of which comprise cluster anions that exhibit a selective organic functionalization of their terminal telluride ligands upon in situ alkylation with the ionic liquid: [Hg 6 Te 6 (Te 2 ) 2 (TeDec) 2 ] 6− (in 1; Dec = decyl) represents the first decylated chalcogenido metalate cluster. A unique heteroleptic functionalization, combining methylation and decylation, was achieved for the second cluster, [Hg 6 Te 6 (Te 2 ) 2 (TeDec)(TeMe)] 6− (in 2; Me = methyl). The third cluster is purely inorganic, but based on the same cluster core architecture: [Hg 4 Te 2 (Te 2 ) 2 (Te 3 ) 2 ] 4− (in 3) comprises a tritelluride unit instead of two HgTeR groups (R = Me, Dec). As a consequence of the long alkyl chains, both at the cluster and at the chargecompensating cations, all three crystal structures are characterized by lamellar assemblies of cations and anions. For further comparison of the properties of the organometallic versus purely inorganic compounds, vibrational and optical properties of crystalline samples of the compounds comprising clusters 1 and 3 were studied by means of infrared, Raman, and UV−visible spectroscopy. The results clearly show the effect of the presence of an organic decoration (in 1) relative to its absence (in 3), reflected by a red shift of the band gap energy (1 → 3) and a replacement of the Te−C bands (in 1) with bands for tritelluride units (in 3).

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Section: Introductionmentioning

confidence: 99%

Ionothermal Approach to Homo- and Heteroleptic Alkylation of Tellurido Mercurate Clusters for Assembly in Lamellar Crystal Structures

Tallu,

Peters,

Friedrich

et al. 2023

Inorg. Chem.

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“…Examples comprise the formation of polybromides, 6 low-valent halides in the system Te–Bi/Al–Cl, 7 the connectivity of (ZnBr 4 ) tetrahedra in bromido zincates, 8 the structure of hexanuclear niobium clusters, 9 or the composition of chalcogenidometallates. 10 These reports mainly focus on halide compounds in ionic liquids, whereas studies on oxides are rare. This finding can be related to the higher lattice energy and the lower solubility of oxides in ionic liquids.…”

Section: Introductionmentioning

confidence: 99%

Oxychloridoselenites(iv) with cubane-derived anions and stepwise chlorine-to-oxygen exchange

Bonnin

Feldmann

2023

Dalton Trans.

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“…The past decades have witnessed the huge advancement of metal chalcogenide clusters, which have well-defined compositions and precise internal/surface structures. − Among them, an important branch is the supertetrahedral clusters resembling regularly shaped segments of cubic sphalerite or hexagonal wurtzite, which have attracted unabated attention. − Early development resulted in a basic supertetrahedral subgroup (Tn) and three other geometrically derivative series from Tn, commonly known as pentasupertetrahedral (Pn), ligand-capped supertetrahedral (Cn), and supersupertetrahedral (Tp,q) clusters. − Because of their unique structural characteristics and chemical composition, these clusters exhibit interesting physicochemical properties, including a semiconductor nature, a quantum-confinement effect, optical nonlinearity, and sensing. − …”

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confidence: 99%

Superhydrophobic Pseudosupertetrahedral Sulfido Metalate Clusters for Constructing Liquid Marbles

et al. 2023

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One pseudopentasupertetrahedral chalcogenidometalate cluster, [(BuSn)3SnCd4S13(OH)]·6(H+DMP) (PPS-1; H+DMP = protonated 3,5-dimethylpiperidine), has been isolated by use of an organotin precursor. They are arranged to generate two types of tetrahedrally patterned cages, which further interconnect to form a diamond network. Owing to the covalent attachment of abundant alkyl groups, PPS-1 exhibits excellent hydrophobicity and could be used as an assembly substance for building liquid marbles.

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Crystalline chalcogenidometalate-based compounds from uncommon reaction media

Abstract: Chalcogenides are one of the most versatile inorganic materials families, further subdivided into a large variety of specific groups of compounds, ranging from neat binary or multinary solids and nanoparticles...

Cited by 7 publications

References 135 publications

Ionothermal Approach to Homo- and Heteroleptic Alkylation of Tellurido Mercurate Clusters for Assembly in Lamellar Crystal Structures

Ionothermal Approach to Homo- and Heteroleptic Alkylation of Tellurido Mercurate Clusters for Assembly in Lamellar Crystal Structures

Oxychloridoselenites(iv) with cubane-derived anions and stepwise chlorine-to-oxygen exchange

Superhydrophobic Pseudosupertetrahedral Sulfido Metalate Clusters for Constructing Liquid Marbles

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