Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
On the nature of main-group polycations: an odyssey
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
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 [en]
Chemistry, Inorganic chemistry
Keyword [sv]
Kemi
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-178ISBN: 91-7178-000-9 (print)OAI: oai:DiVA.org:kth-178DiVA: diva2:7781
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
List of papers
1. Ab initio Calculations on Bismuth Cluster Polycations
Open this publication in new window or tab >>Ab initio Calculations on Bismuth Cluster Polycations
Show others...
2001 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 7, no 13, 2821-2828 p.Article in journal (Refereed) Published
Abstract [en]

Ab initio calculations on bismuth polycationic species of the types Bi-n((n-2)+), Bi-n((n-4)+), and Bi-n((n-6)+) (n = 3 -12) were performed at the Hartree -Fock and density functional theory levels in order to investigate their general properties and the applicability of Wade's rules on bismuth polycations. Some exceptions to Wade's rules were encountered, and, moreover, several predicted and calculated minima shaw only meta-stable behavior. The bonding in bismuth polycations is characterized by a high degree of electron delocalization and "three-dimensional aromaticity".

Keyword
ab initio calculations; bismuth; cluster compounds; ELF (electron localization function)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5067 (URN)10.1002/1521-3765(20010702)7:13<2821::AID-CHEM2821>3.0.CO;2-Y (DOI)000169765800013 ()
Note
QC 20100825Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
2. Sb8[GaCl4]2: Isolation of a Homopolyatomic Antimony Cation
Open this publication in new window or tab >>Sb8[GaCl4]2: Isolation of a Homopolyatomic Antimony Cation
2004 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 43, no 19, 2540-2543 p.Article in journal (Refereed) Published
Abstract [en]

An almost perfect square-antiprismatic geometry is observed for Sb 82+ (see picture), as predicted by the Wade rules. The title compound, which was synthesized in benzene at room temperature, represents the first homopolyatomic antimony cation and has Sb-Sb bond lengths of 285-300 pm.

Keyword
Antimony, Cluster compounds, Polycations, Raman spectroscopy
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5068 (URN)10.1002/anie.200353578 (DOI)000221307600017 ()2-s2.0-4544280172 (Scopus ID)
Note
QC 20100929Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
3. Improvements of and insights into the isolation of bismuth polycations from benzene solution - Single-crystal structure determinations of Bi-8[GaCl4](2) and Bi-5[GaCl4](3)
Open this publication in new window or tab >>Improvements of and insights into the isolation of bismuth polycations from benzene solution - Single-crystal structure determinations of Bi-8[GaCl4](2) and Bi-5[GaCl4](3)
2005 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, Vol. 2005, no 4, 670-675 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis, crystal growth and structure are reported for the two salts Bi-5[GaCl4](3) and Bi-8[GaCl4](2). The compounds are prepared from a solution of BiCl3 and GaCl3 in benzene, using gallium metal as reducing agent. Bi-8[GaCl4](2) contains a Bi-8(2+) polycation that, essentially, adopts an ideal square antiprismatic geometry. The compound crystallizes in the P6(3) space group; a = 17.760(2) Angstrom and c = 12.979(3) Angstrom. Bi-5[GaCl4](3) crystallizes in the R3c space group, a = 11.814(2) Angstrom, c = 29.974(3) Angstrom, and contains a Bi-5(3+) cation adopting a trigonalbipyramidal geometry. The cation is slightly distorted from the ideal D-3h symmetry.

Keyword
bismuth, cluster compounds, polycations, subvalent compounds
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5069 (URN)10.1002/ejic.200400466 (DOI)000227257100007 ()2-s2.0-14844307586 (Scopus ID)
Note
QC 20100917Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
4. Tetratellurium Bis[heptachlorodigallate(III)], Te4[Ga2Cl7]2
Open this publication in new window or tab >>Tetratellurium Bis[heptachlorodigallate(III)], Te4[Ga2Cl7]2
2005 (English)In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, Vol. 61, no 2, 118-119 p.Article in journal (Refereed) Published
Abstract [en]

Te4[Ga2Cl7]2 has been isolated from GaCl3-benzene media and its structure determined. The structure features a centrosymmetric square-planar Te42+ cation and staggered [Ga2Cl7]- anions, consisting of two corner-sharing GaCl4 tetrahedra. The chlorine bridge between the Ga atoms in the anion is bent. The title compound is isotypic with Te 4[Al2Cl7]2.

Keyword
Chemical Bonds, Conformations, Crystal Symmetry, Gallium Compounds, Mixtures, Raman Spectroscopy, Tellurium Compounds
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5070 (URN)10.1107/S1600536805001960 (DOI)000226692400004 ()2-s2.0-18544385185 (Scopus ID)
Note
QC 20101021Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
5. Synthesis of main group polycations in molten and pseudo-molten GaBr3 media
Open this publication in new window or tab >>Synthesis of main group polycations in molten and pseudo-molten GaBr3 media
Show others...
2005 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, 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.

Keyword
Antimony, Bismuth, Cluster compounds, Tellurium
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5071 (URN)10.1002/ejic.200500161 (DOI)000234237900007 ()2-s2.0-29344456611 (Scopus ID)
Note
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: 2017-12-05Bibliographically approved
6. Anionic Diversity in Iodobismuthate Chemistry
Open this publication in new window or tab >>Anionic Diversity in Iodobismuthate Chemistry
2005 (English)In: Zeitschrift für Anorganische und Allgemeines Chemie, ISSN 0044-2313, E-ISSN 1521-3749, Vol. 631, no 8, 1497-1501 p.Article in journal (Refereed) Published
Abstract [en]

 Three salts containing different iodobismuthate anions have been synthesized. [(CH3)(2)NH2](3)[BiI6] was prepared by oxidation of bismuth by iodine in N,N-dimethylformamide. [(CH3)(2)NH2](3)[BiI6] crystallizes in the space group R3 with a = 30.760(3) angstrom and c = 8.8039(5) angstrom and contains monomeric [BiI6](3-) anions. The hydrate Na-4[Bi2I10] (.) 14H(2)O was prepared by the oxidation of bismuth using iodine in acetonitrile in the presence of NaI. Na-4[Bi2I10](.)14H(2)O crystallizes in the space group C2/m with a = 12.875(2) angstrom, b = 16.177(2) angstrom, c = 9.904(2) angstrom and beta = 106.57(6)degrees. The structure contains dimeric [Bi2I10](4-) anions and rows of sodium ions, with bridging water molecules. The hydrate [Na{(CH3)(2)NCHO}(2)(H2O)](3)[Bi2I9] was prepared by dissolution of Na-4[Bi2I10] (.) 14H(2)O in N,N-dimethylformamide and crystallizes in the space group P1 with a = 13.2309(13) angstrom, b = 13.3791(14) angstrom, c = 18.722(2) angstrom, alpha = 70.338(9)degrees, beta = 72.651(9)degrees and gamma = 62.183(5). The structure contains dimeric [Bi2I9](3-) anions and cationic polymers, [Na{(CH3)(2)NCHO}(2)(H2O)](+).

Keyword
bismuth, crystal structure, iodine
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5072 (URN)10.1002/zaac.200400559 (DOI)000229778300029 ()2-s2.0-20444372964 (Scopus ID)
Note
QC 20100830 Uppdaterat från in press till published (20100830)Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
7. Electronic Structure of Bismuth Subiodides
Open this publication in new window or tab >>Electronic Structure of Bismuth Subiodides
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5073 (URN)
Note
QC 20101021Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2010-10-21Bibliographically approved
8. Novel Compounds Sn14In10P22I8 and Sn14In10P21.2I8 with Clathrate-I Structure: Synthesis and Crystal and Electronic Structure
Open this publication in new window or tab >>Novel Compounds Sn14In10P22I8 and Sn14In10P21.2I8 with Clathrate-I Structure: Synthesis and Crystal and Electronic Structure
Show others...
2001 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 161, no 2, 232-242 p.Article in journal (Refereed) Published
Abstract [en]

Two new supramolecular pnictidehalides Sn10In14P22I8 (I) anti Sn14In10P21.2I8 (II) have been synthesized using a standard ampoule technique. Both compounds possess the clathrate I type of structure. I crystallizes in the cubic space group Pm (3) over barn (No. 223) with the unit cell parameter a = 11.0450(7) (Z = 1) while II reveals a complicated superstructure (space group P4(2)/m (No. 84), a = 24.745(3) Angstrom, c = 11.067(1) Angstrom, Z = 5) resulting from the partial ordering of vacancies at phosphorus sites. The crystal structures have been solved based on single-crystal X-ray diffraction data sets (omega -2 theta) scans, least-squares refinement against F-2) to R = 0.0376 (Sn10In14P22I8) and R = 0.0569 (Sn14In10P21.2I8). In both structures metal anti phosphorus atoms form a cationic clathrate I framework hosting iodine atoms in the cavities. The composition of both phases complies with the Zintl-Klemm formalism which justifies the existence of vacancies in the structure of II. The Sn-119 Mossbauer spectroscopy data together with the results of the band structure calculations suggest that the electron density on tin atoms is reduced in favor of bands, which lie just below the Fermi level and must define electronic properties of the compounds in question. The differences in the crystal and electronic structures of the cationic tin clathrates are discussed.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5074 (URN)10.1006/jssc.2001.9304 (DOI)000172466400008 ()
Note
QC 20101021Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved
9. 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
Open this publication in new window or tab >>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
Show others...
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.

Keyword
arsenic, band structure, host-guest systems, mercury, solid-state structures, supramolecular chemistry
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-5075 (URN)10.1002/chem.200204687 (DOI)000184479300003 ()
Note
QC 20100906Available from: 2005-04-26 Created: 2005-04-26 Last updated: 2017-12-05Bibliographically approved

Open Access in DiVA

fulltext(1166 kB)1512 downloads
File information
File name FULLTEXT01.pdfFile size 1166 kBChecksum MD5
571159dd8e88227698b79c829bfc8b9c8628dd322edad0a485ed2c3908a12664a85569c1
Type fulltextMimetype application/pdf

Search in DiVA

By author/editor
Lindsjö, Martin
By organisation
Chemistry
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar
Total: 1512 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 760 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf