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Synthesis of main group polycations in molten and pseudo-molten GaBr3 media
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
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2005 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-0682, no 24, 4907-4913 p.Article in journal (Refereed) Published
Abstract [en]

 The prospects of synthesizing polycationic species using GaBr3 in benzene solution at room temperature have been investigated. The salts Bi-8[GaBr4](2), Sb-8[GaBr4](2) and Te-4- [Ga2Br7](2) have been isolated and characterized. The first two compounds are isotypic with Sb-8[GaCl4](2), crystallize in the space group Pna2(1), and feature square anti-prismatic E-8(2+) polycations (E = Sb, Bi). Unit-cell parameters for Bi-8[GaBr4](2) are a = 18.3014(10) angstrom, b = 10.3391(6) angstrom and c = 13.5763(7) angstrom, and for Sb-8[GaBr4](2); a = 18.096(2) angstrom, b = 10.1572(9) angstrom and c = 13.2168(10) angstrom. Te-4[Ga2Br7](2) crystallizes in the space group P2(1)/c with a = 10.1600(9) angstrom, b = 10.8314(9) angstrom, c = 13.8922(10) angstrom and beta = 99.182(7)degrees, and features a square-planar Te-4(2+) polycation. The compound Bi-5[GaBr4](3) has been synthesized from molten GaBr3 and characterized by using powder diffractometry in space group Fm-3c; a = 17.6263(8) angstrom. The structure model for this compound suggests the included Bi-5(3+) cations to be practically freely oriented within its cavities in the solid phase.

Place, publisher, year, edition, pages
2005. no 24, 4907-4913 p.
Keyword [en]
Antimony, Bismuth, Cluster compounds, Tellurium
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-5071DOI: 10.1002/ejic.200500161ISI: 000234237900007ScopusID: 2-s2.0-29344456611OAI: diva2:7776
QC 20101001. Uppdaterad från Submitted till Published (20101001). Tidigare titel: "Synthesis of Main Group Polycations in GaBr3–Benzene Media".Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2010-10-01Bibliographically approved
In thesis
1. On the nature of main-group polycations: an odyssey
Open this publication in new window or tab >>On the nature of main-group polycations: an odyssey
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Compounds containing main-group clusters, with focus on bismuth polycations, have been synthesized and characterized using X-ray diffraction and spectroscopic methods.

Six new compounds have been isolated from synthesis in GaX3-arene media; Bi8[GaCl4]2, Bi8 [GaBr4]2, Sb8[GaCl4]2, Sb8[GaBr4]2, Te4[Ga2Cl7]2 and Te4[Ga2Br7]2. Sb2+ 8 is the first homopolyatomic antimony cation to be isolated. The cation forms a square antiprism, in correlation with Wade’s rules, and displays a significant difference in length between the inter-square and intra-square Sb–Sb distances. The geometries of the Sb2+ 8 cations in Sb8[GaCl4]2 and Sb8[GaBr4]2 are in excellent agreement; the average intra-square and intersquare Sb–Sb distances are 2.87 Å and 2.97 Å, respectively.

A very strong Raman band attributed to Sb2+8 is found at 180 cm-1. The Bi2+8 (square antiprismatic) and Te2+4 (squareplanar) polycations are known from earlier compounds. The Bi–Bi distances in Bi8[GaCl4]2 (3.07–3.12 Å) are in general agreement with previous structures, while the Bi–Bi distances of Bi8[GaBr4]2 (2.92–3.18 Å) display a wider distrubution than previously observed. The Te–Te distances of the cations of Te4[Ga2Cl7]2 and Te4[Ga2Br7]2 are 2.66 and 2.67 Å, respectively.

Quantum chemical calculations on bismuth polycations show that all species predicted byWade’s rules are local minima on a potential energy surface. The cation–anion interactions have been considered for salts containing bismuth polycations and it has been confirmed that such interactions have a major influence on the polycation stability.

The new compound Bi16I4 has been isolated from molten Bil3. The structure consists of polymerized Bi16I4 molecules forming infinite ribbons and is very similar to the structure of the known metal-rich bismuth iodides, Bi14I4 and Bi18I4.

DFT calculations predict all three compounds to be metallic conductors, while Bi4I4 is a semiconductor.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. x, 104 p.
Trita-OOK, ISSN 0348-825X ; 1077
Chemistry, Inorganic chemistry, Kemi
National Category
Chemical Sciences
urn:nbn:se:kth:diva-178 (URN)91-7178-000-9 (ISBN)
Public defence
2005-04-29, sal D3, Lindstedtsvägen 5, Stockholm, 13:00 (English)
QC 20101021Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2010-10-21Bibliographically approved

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