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Synthesis and Crystal Structure of the Solid Solution Co-3(SeO3)(3-x)(PO3OH)(x)(H2O) Involving Crystallographic Split Positions of Se4+ and P5+
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
2013 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 52, no 20, 11792-11797 p.Article in journal (Refereed) Published
Abstract [en]

Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co-3(SeO3)(3-x)(PO3OH)(x)(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se4+ and P5+ share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P5+. The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 degrees C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) mu(B) per Co atom was observed.

Place, publisher, year, edition, pages
2013. Vol. 52, no 20, 11792-11797 p.
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-96601DOI: 10.1021/ic401111zISI: 000326065600016OAI: oai:DiVA.org:su-96601DiVA: diva2:666972
Note

AuthorCount:2;

Available from: 2013-11-25 Created: 2013-11-25 Last updated: 2017-12-06Bibliographically approved
In thesis
1. The Role of Tetrahedral Building Blocks in Low-Dimensional Oxohalide Materials
Open this publication in new window or tab >>The Role of Tetrahedral Building Blocks in Low-Dimensional Oxohalide Materials
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The structural architecture found in low-dimensional materials can lead to a number of interesting physical properties including anisotropic conductivity, magnetic frustration and non-linear optical properties. There is no standard synthesis concept described thus far to apply when searching for new low-dimensional compounds, and therefore control on the design of the new materials is of great importance.This thesis describes the synthesis, crystal structure and characterization of some new transition metal oxohalide compounds containing p-elements having a stereochemically active lone-pair. First row transition metal cations have been used in combination with SeIV, SbIII and TeIV ions as lone-pair elements and Cl- and Br- as halide ions. The lone-pairs do not participate in covalent bonding and are responsible for an asymmetric one-sided coordination. Lone-pair elements in combination with halide ions have shown to be powerful structural spacers that can confine transition metal building blocks into low-dimensional arrangements. The halide ions and lone-pairs reside in non-bonded crystal volumes where they interact through weak van der Waals forces. The transition metal atoms are most often arranged to form sheets, chains or small clusters; most commonly layered compounds are formed.To further explore the chemical system and to separate the transition metal entities even more the possibility to include tetrahedral building blocks such as phosphate-, silicate-, sulphate- and vanadate building blocks into this class of compounds has been investigated. Tetrahedral building blocks are well known for their ability of segmenting structural arrangements by corner sharing, which often leads to the formation of open framework structures. The inclusion of tetrahedral building blocks led to the discovery of interesting structural features such as complex hydrogen bonding, formation of unusual solid solutions or faulted stacking of layers.Compounds for which phase pure material could be synthesized have been characterized in terms of their magnetic properties. Most compounds were found to have antiferromagnetic spin interactions and indications of magnetic frustration could be observed in some of them.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2014. 60 p.
Keyword
Lone-pair elements, crystal structure, low-dimensional compounds, oxohalides
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-108160 (URN)978-91-7649-014-3 (ISBN)
Public defence
2014-11-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockhom, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 6: Manuscript. Paper 9: Manuscript. Paper 10: Manuscript.

Available from: 2014-10-22 Created: 2014-10-13 Last updated: 2014-11-18Bibliographically approved

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