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Coordinated and clathrated guests in the (3)(infinity)[Hg6As4](4+) bicompartmental framework: Synthesis, crystal and electronic structure, and properties of the novel supramolecular complexes [Hg6As4](CrBr6)Br and [Hg6As4](FeBr6)Hg-0.6
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.
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2003 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 9, no 14, 3201-3208 p.Article in journal (Refereed) Published
Abstract [en]

Two new supramolecular complexes [Hg6As4](CrBr6)Br (1) and [Hg6As4](FeBr6)Hg-0.6 (2) have been prepared by the standard ampoule technique and their crystal structures determined. Both crystallize in the cubic space group PO with the unit cell parameter a = 12.275(1) (1) and 12.332(1) Angstrom (2), and Z = 4. Their structures consist of bicompartmental, three-dimensional [Hg6As4](4+) frameworks with cavities of two different sizes occupied by guest anions of different type. ne bigger cavities are filled with the octahedral MBr6n- ions (M = Cr or Fe; n = 3 or 4), whereas the smaller cavities trap either Br- ions (1) or Hg-0 (2). The analysis of the host-guest contacts has allowed a classification of the octahedral guests as coordinated and the monatomic guests as clathrated. Magnetic measurements and ESR spectroscopy data have given information about the interaction between the host and guests. Band structure calculations (HF and hybrid DFT level) indicate that both 1 and 2 are non-metallic, with a band gap of approximately 1.5 eV (B3LYP), and that the interaction between the host and guests is of predominantly electrostatic character. It is shown that though the electrostatic host-guest interaction is weak it plays an important role in assembling the perfectly ordered supramolecular architectures.

Place, publisher, year, edition, pages
2003. Vol. 9, no 14, 3201-3208 p.
Keyword [en]
arsenic, band structure, host-guest systems, mercury, solid-state structures, supramolecular chemistry
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-5075DOI: 10.1002/chem.200204687ISI: 000184479300003OAI: oai:DiVA.org:kth-5075DiVA: diva2:7780
Note
QC 20100906Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically 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.
Series
Trita-OOK, ISSN 0348-825X ; 1077
Keyword
Chemistry, Inorganic chemistry, Kemi
National Category
Chemical Sciences
Identifiers
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)
Opponent
Supervisors
Note
QC 20101021Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2010-10-21Bibliographically approved

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