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A new synthetic strategy for low-dimensional compounds: Lone pair cations and alkaline earth spacers
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Complex transition metals oxyhalides containing a lone pair element, such as tellurium (IV), form an attractive research field because there is a high probability of finding new low-dimensionally arranged compounds and, particularly, a low-dimensionally arranged transition metals substructures, leading to interesting physical properties. Tellurium (IV) can drive the formation of many unusual structures because of its stereochemically active lone pair electrons, E. It commonly takes a coordination of three or four oxygen atoms to form either a TeO3E square pyramid or a TeO3+1E trigonal bipyramid. These lone pairs are very important players involved in lowering the dimensionality of crystal structures. Previous studies in transition metal tellurium (IV) oxohalide quarternary systems revealed a family of compounds, many of which exhibit interesting properties e.g. magnetic frustration. The unique point of this thesis is to employ alkaline earth elements (AE) to augment this ability of lone pair elements to lower the dimensionality of the transition metal arrangements. By this double usage of “chemical scissors” (a lone pair element used in conjunction with alkaline earth elements) we obtained new types of low-dimensionally arranged compounds.

This thesis is focused on the syntheses and characterization of a series of compounds in the pentanary (five components) system AE-TeIV-TM-O-X (AE=alkaline earth metal, TM=transition metal and X=halogen), in which nine new compounds were found. The crystal structures of each of these compounds were determined by the single crystal X-ray diffraction data.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi , 2008. , 58 p.
Keyword [en]
Alkaline earth, Lone pair elements, Low-dimensional compounds
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-7284ISBN: 978-91-7155-538-0 (print)OAI: oai:DiVA.org:su-7284DiVA: diva2:197982
Public defence
2008-01-28, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00
Opponent
Supervisors
Available from: 2008-01-08 Created: 2008-01-08Bibliographically approved
List of papers
1. Ca2CuTe4O10Cl2, a new synthetic tellurium(IV) oxochloride
Open this publication in new window or tab >>Ca2CuTe4O10Cl2, a new synthetic tellurium(IV) oxochloride
2005 In: Acta Cryst., Vol. C, no 61, i106-i108 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24633 (URN)
Note
Part of urn:nbn:se:su:diva-7284Available from: 2008-01-08 Created: 2008-01-08Bibliographically approved
2. Crystal structure and magnetic properties of the coupled spin dimer compound
Open this publication in new window or tab >>Crystal structure and magnetic properties of the coupled spin dimer compound
2006 In: J. of Solid State Chemistry, Vol. 179, 3763-3767 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24634 (URN)
Note
Part of urn:nbn:se:su:diva-7284Available from: 2008-01-08 Created: 2008-01-08Bibliographically approved
3. Sr2Cu2TeO6Br2: Honeycomb layers of Cu(II) ions
Open this publication in new window or tab >>Sr2Cu2TeO6Br2: Honeycomb layers of Cu(II) ions
2006 In: Acta Cryst., Vol. C, no 62, i38-i40 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24635 (URN)
Note
Part of urn:nbn:se:su:diva-7284Available from: 2008-01-08 Created: 2008-01-08Bibliographically approved
4. The solid solution Co3.6Mg1.4Cl2(TeO3)4
Open this publication in new window or tab >>The solid solution Co3.6Mg1.4Cl2(TeO3)4
2007 In: Acta Cryst., Vol. E, no 63, i146-i147 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24636 (URN)
Note
Part of urn:nbn:se:su:diva-7284Available from: 2008-01-08 Created: 2008-01-08Bibliographically approved
5. Single-Crystal X-ray Study of Ba2Cu2Te4O11Br2 and Its Incommensurately Modulated Superstructure Companion
Open this publication in new window or tab >>Single-Crystal X-ray Study of Ba2Cu2Te4O11Br2 and Its Incommensurately Modulated Superstructure Companion
2008 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 14, no 11, 3434-3441 p.Article in journal (Refereed) Published
Abstract [en]

Compounds containing lone-pair elements such as TeIV are very interesting from the structural point of view, as the lone-pair nonbonding regions create low-dimensional geometrical arrangements. We have synthesized two new compounds with these features—Ba2Cu2Te4O11Br2 (I) and Ba2Cu2Te4O11−δ(OH)2δBr2 (II, δ≈0.57)—as members of the AE-M-Te-O-X (AE=alkaline-earth metal, M=transition metal, X=halide) family of compounds by solid-state reactions. Preliminary single-crystal X-ray analysis indicated that compound I crystallizes in the orthorhombic system, but attempts at refinement proved unsatisfactory. Closer inspection of the reciprocal lattice revealed systematic, non-crystallographic absences that indicate twinning. The structure is in fact triclinic, space group C (equivalent to P), with unit cell parameters (at 120 K) of a=10.9027(9), b=15.0864(7), c=9.379(2) Å, β=106.8947°. It is layered and built from [TeO3E] tetrahedra, [TeO3+1E] trigonal bipyramids (where E is the lone pair of TeIV), [CuO4] squares and irregular [BaO10Br] polyhedra. The crystal structure of II shows the same basic structure as I but contains additional oxygen, probably in the form of OH groups. The presence of satellites reveals that ordering on this O site creates an incommensurate modulation, primarily affecting Br and Te. The modulated structure of II was solved in the triclinic superspace group X(αβγ)0 with the vector q≈1/16 c*.

Keyword
alkaline earth metals, layered compounds, solid-state reactions, structure elucidation, tellurium
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:su:diva-24637 (URN)10.1002/chem.200701527 (DOI)000255230200023 ()
Available from: 2008-01-08 Created: 2008-01-08 Last updated: 2011-02-11Bibliographically approved
6. Helical chains of [MO5Cl] octahedra – Three compounds in the new family AEM2Te3O8Cl2 (AE = Ca, Sr and M = Co, Ni):  
Open this publication in new window or tab >>Helical chains of [MO5Cl] octahedra – Three compounds in the new family AEM2Te3O8Cl2 (AE = Ca, Sr and M = Co, Ni):  
2009 (English)In: Solid State Sciences, ISSN 1293-2558, Vol. 11, no 1, 13-17 p.Article in journal (Refereed) Published
Abstract [en]

The compounds CaCo2Te3O8Cl2, SrCo2Te3O8Cl2 and SrNi2Te3O8Cl2 were synthesized via solid–gas reactions and investigated using single-crystal X-ray diffraction. While the compound CaCo2Te3O8Cl2 formed large enough single crystals to allow for a detailed structural analysis, crystals of the Sr-containing compounds yielded evidence that they are isostructural. CaCo2Te3O8Cl2 crystallizes in the monoclinic system, space group P21/c, a = 6.537(2) Å, b = 9.088(2) Å, c = 19.500(9) Å, β = 113.36(4)°, Z = 4. It exhibits [CoO5Cl] helical chains along the [010] direction, connected by [CaO8] polyhedra, [TeO3E] tetrahedra and [TeO4E] trigonal bipyramids (the lone pair of electrons on TeIV is designated as E) to form a layer. The layers are held together only by weak van der Waals forces; the shortest interlayer distance is a TeCl contact of 3.432(4) Å.

Keyword
Layered structure; Lone pair compounds; Chemical scissors
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-24638 (URN)10.1016/j.solidstatesciences.2008.04.009 (DOI)000262753300001 ()
Available from: 2008-01-08 Created: 2008-01-08 Last updated: 2011-06-14Bibliographically approved

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