Syntheses and Characterizations

Scharfe, Sandra; Fässler, Thomas F.; Eychmüller, Alexander; Banin, Uri; Dehnen, Stefanie; Eichhöfer, Andreas; Corrigan, John F.; Fuhr, Olaf; Fenske, Dieter; Schmid, Günter; Krylova, Galyna; Bodnarchuk, Maryna I.; Tromsdorf, Ulrich I.; Shevchenko, Elena V.; Talapin, Dmitri V.; Weller, Horst

doi:10.1002/9783527631544.ch3

Cited by 7 publications

(6 citation statements)

References 1,072 publications

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“…Endohedral anionic clusters of germanium, tin, and lead are more common and, in contrast to fullerenes, display an immense structural diversity; however, the mechanism of their formation has still not been sufficiently explored. [8,9] The nature of the chemical bonds in both species differs, even though similarities have been recognized here as well. [10,11] Whereas localized covalent single and double bonds are typical for fullerenes and fullerides, a concept of delocalized bonds is used for the description of polyhedral Zintl anions.…”

Section: Introductionmentioning

confidence: 85%

“…[8,9] For cluster 1a, 31 (Figure 1c) are reported in the literature. [29,30] The anions of compound 1a and 3a are closely surrounded by potassium cations.…”

Section: Introductionmentioning

confidence: 94%

“…Reactions of main-group-element compounds with tetrel-atom Zintl anions usually result in the addition of ligands to the cluster with formation of an exo bond, [9] but transition-metal compounds lead to capped, endohedrally filled, or capped endohedral clusters. [8] Fullerenes coordinate to transition-metal atoms through a double bond or in an η 5 fashion through a fivemembered ring (Figure 1). [13,14] In contrast, the coordination of E 9 clusters to transition metals is so far limited to the open square face of the nido-shaped polyhedron, and only two examples in which a transition metal is coordinated in an η 5 fashion are known in the literature.…”

Section: Introductionmentioning

confidence: 99%

“…[8] Polyhedral nine-atom anions [E 9 ] x-(E = Si-Pb; x = 3, 4) react in two opposing ways with main-group elements and transition-metal compounds, respectively. Reactions of main-group-element compounds with tetrel-atom Zintl anions usually result in the addition of ligands to the cluster with formation of an exo bond, [9] but transition-metal compounds lead to capped, endohedrally filled, or capped endohedral clusters.…”

Section: Introductionmentioning

confidence: 99%

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Varying Bonding Modes of the Zintl Ion [Ge₉]^4– in Cu^I Complexes: Syntheses and Structures of [Cu(η⁴‐Ge₉)(PR₃)]^3– (R = iPr, Cy) and [Cu(η⁴‐Ge₉)(η¹‐Ge₉)]^7–

Scharfe

Fässler

2010

Eur J Inorg Chem

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Three novel Cu‐capped Ge9 clusters were synthesized from K4Ge9 and phosphane‐stabilized copper(I) compounds CuCl(PR3) with R = isopropyl (iPr) or cyclohexyl (Cy). Reactions in N,N‐dimethylformamide (dmf) at ambient temperature resulted in the isolation of [Cu(η4‐Ge9)(PCy3)]3– as a [K([2.2]crypt)] salt ([2.2]crypt: 1,7,10,16‐tetraoxa‐4,13‐diazacyclooctadecane). From solutions of [Cu(η4‐Ge9)(PiPr3)]3– in liquid ammonia, the anion was isolated when the reaction mixture was stored at –70 °C. Under the same reaction conditions but at a temperature of –40 °C the cluster [Cu(η4‐Ge9)(η1‐Ge9)]7– crystallized in the presence of [2.2.2]crypt(4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosan)or [2.2]crypt. The ligand‐free intermetalloid cluster [Cu(η4‐Ge9)(η1‐Ge9)]7– is a unique example in which two differently bonded Ge9 units are linked by a transition‐metal atom. This cluster complex remarkably demonstrates the ability of homoatomic polyanions to bind in different modes to the same transition‐metal atom. One Ge9 nido cluster binds to the copper atom by means of its open square face, whereas the second Ge9 nido cluster is coordinated through one lone pair as a two‐electron σ donor. The key role of the flexible electron‐donor properties of [Ge9]4– in the reaction path towards the formation of intermetalliod clusters is discussed.

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Section: Introductionmentioning

confidence: 85%

“…[8,9] For cluster 1a, 31 (Figure 1c) are reported in the literature. [29,30] The anions of compound 1a and 3a are closely surrounded by potassium cations.…”

Section: Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Varying Bonding Modes of the Zintl Ion [Ge₉]^4– in Cu^I Complexes: Syntheses and Structures of [Cu(η⁴‐Ge₉)(PR₃)]^3– (R = iPr, Cy) and [Cu(η⁴‐Ge₉)(η¹‐Ge₉)]^7–

Scharfe

Fässler

2010

Eur J Inorg Chem

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“…Consequently, there are a particularly large number of surface atoms that have different properties than atoms within a particle. The bonds of the surface atoms are nonsaturated because the surface lacks the neighboring atoms to which bonds are formed inside the particle . This leads to tension.…”

Section: Discussionmentioning

confidence: 99%

Rational Design of the Electronic Structure of CdS Nanopowders

2023

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In this study, various techniques, such as energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Raman spectroscopy, and spectrophotometry, were used to analyze the properties of nanometric CdS particles synthesized with varying precursor concentrations. EDX analysis revealed the nonstoichiometric composition manifested by an increase in the Cd/S ratio from 1.02 up to 1.43 with increasing precursor concentration. The growth of lattice parameters and unit cell volume accompanying preferential crystallization of the hexagonal phase along with an increasing Cd/S ratio was confirmed by XRD analysis. This indicated the presence of interstitial cadmium in nonstoichiometric Cd 1+x S. The formation of shallow Cd i donor levels below the bottom edge of the conduction band impacts the bang-gap energy; a decrease from 2.56 to 2.21 eV along with increasing nonstoichiometry was observed. This is accompanied by a widening of the range of absorption of light, which creates conditions that can lead to an increase in the efficiency of redox reactions in photochemical processes.

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Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

et al. 2011

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Lange Zeit betrachtete man die Zintl‐Ionen der Elemente der 14. und 15. Gruppe für bemerkenswerte, in der Festkörperchemie angesiedelte Spezies, die einerseits durch ihre unerwarteten Zusammensetzungen und faszinierenden Strukturen auffielen, andererseits aber von nur eingeschränkter Bedeutung waren. Neue Aufmerksamkeit erfuhren die Zintl‐Ionen, als man feststellte, dass diese in festen Zintl‐Phasen vorgeformten Spezies aus ihrem Kristallverband extrahiert, in geeigneten Solventien gelöst und damit als Reaktanten und Bausteine in der Lösungschemie verfügbar gemacht werden können. Der steile Anstieg von Forschungsaktivitäten in diesem Gebiet führte zu einer Fülle neuer Verbindungen, beispielsweise durch Funktionalisierung dieser Zintl‐Ionen mit organischen Gruppen und metallorganischen Fragmenten, durch oxidative Kupplungsreaktionen unter Bildung von Dimeren, Oligomeren und Polymeren oder durch Einlagerung von Metallatomen, wobei endohedrale Cluster und intermetallische Verbindungen gebildet werden, von denen einige vielversprechende Perspektiven für Anwendungen in den Materialwissenschaften zeigen. Dieser Aufsatz berichtet über die enormen Fortschritte in der Chemie der Zintl‐Ionen mit Hauptaugenmerk auf deren Herstellung, Eigenschaften, Strukturen und theoretischer Beschreibung.

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Syntheses and Characterizations

Cited by 7 publications

References 1,072 publications

Varying Bonding Modes of the Zintl Ion [Ge₉]^4– in Cu^I Complexes: Syntheses and Structures of [Cu(η⁴‐Ge₉)(PR₃)]^3– (R = iPr, Cy) and [Cu(η⁴‐Ge₉)(η¹‐Ge₉)]^7–

Varying Bonding Modes of the Zintl Ion [Ge₉]^4– in Cu^I Complexes: Syntheses and Structures of [Cu(η⁴‐Ge₉)(PR₃)]^3– (R = iPr, Cy) and [Cu(η⁴‐Ge₉)(η¹‐Ge₉)]^7–

Rational Design of the Electronic Structure of CdS Nanopowders

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

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Syntheses and Characterizations

Cited by 7 publications

References 1,072 publications

Varying Bonding Modes of the Zintl Ion [Ge9]4– in CuI Complexes: Syntheses and Structures of [Cu(η4‐Ge9)(PR3)]3– (R = iPr, Cy) and [Cu(η4‐Ge9)(η1‐Ge9)]7–

Varying Bonding Modes of the Zintl Ion [Ge9]4– in CuI Complexes: Syntheses and Structures of [Cu(η4‐Ge9)(PR3)]3– (R = iPr, Cy) and [Cu(η4‐Ge9)(η1‐Ge9)]7–

Rational Design of the Electronic Structure of CdS Nanopowders

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

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Varying Bonding Modes of the Zintl Ion [Ge₉]^4– in Cu^I Complexes: Syntheses and Structures of [Cu(η⁴‐Ge₉)(PR₃)]^3– (R = iPr, Cy) and [Cu(η⁴‐Ge₉)(η¹‐Ge₉)]^7–

Varying Bonding Modes of the Zintl Ion [Ge₉]^4– in Cu^I Complexes: Syntheses and Structures of [Cu(η⁴‐Ge₉)(PR₃)]^3– (R = iPr, Cy) and [Cu(η⁴‐Ge₉)(η¹‐Ge₉)]^7–