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Crystal Structure and Magnetic Properties of the S=1/2 Quantum Spin System Cu-7(TeO3)(6)F-2 with Mixed Dimensionality
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0002-0323-0210
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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2014 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 53, no 14, 7661-7667 p.Article in journal (Refereed) Published
Abstract [en]

The new oxofluoride Cu-7(TeO3)(6)F-2 has been synthesized by hydrothermal synthesis. It crystallizes in the triclinic system, space group P (1) over bar. The crystal structure constitutes a Cu-O framework with channels extending along [001] where the F- ions and the stereochernically active lone-pairs on Te4+ are located. From magnetic susceptibility, specific heat, and Raman scattering measurements we find evidence that the magnetic degrees of freedom of the Cu-O-Cu segments in Cu-7(TeO3)(6)F-2 lead to a mixed dimensionality with single Cu S = 1/2 moments wealdy coupled to spin-chain fragments. Due to the weaker coupling of the single moments, strong fluctuations exist at elevated temperatures, and long-range magnetic ordering evolves at comparably low temperatures (T-N = 15 K).

Place, publisher, year, edition, pages
2014. Vol. 53, no 14, 7661-7667 p.
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-106923DOI: 10.1021/ic5009686ISI: 000339472000066OAI: oai:DiVA.org:su-106923DiVA: diva2:741917
Note

AuthorCount:7;

Available from: 2014-08-29 Created: 2014-08-27 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Transition metal oxofluorides comprising lone pair elements: Synthesis and Characterization
Open this publication in new window or tab >>Transition metal oxofluorides comprising lone pair elements: Synthesis and Characterization
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Within the family of transition metal oxochlorides/bromides containing lone pair elements, the transition metal cations often adopt a low-dimensional arrangement such as 2D layers, 1D chains or 0D clusters. The reduced dimensionality is attributed to the presence of stereochemically active lone pairs which are positioned in the non-bonding orbital and will not participate in bond formation and instead act as structural spacers that help to separate coordination polyhedra around transition metal cations from forming three dimensional networks. On the other hand, the chlorine and bromine ions also play an important role to open up the crystal structure because of their low coordination number. However, fluorine has been rarely used in this concept due to the difficulties in synthesis.

This thesis is focused on finding new compounds in the M-L-O-F system (M = transition metal cation, L= p-block lone pair elements such as Te4+, Se4+, or Sb3+) in order to study the structural character of fluorine. Hydrothermal reactions have been adopted instead of conventional chemical transport reactions that are commonly used for synthesizing compounds in the M-L-O-(Cl, Br) family. A total of 8 new transition metal oxofluorides containing lone pair elements have been synthesized and their structures have been determined via single crystal X-ray diffraction. Bond valence sum calculations are used to distinguish in between fluorine and oxygen due to their very similar X-ray scattering factors.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2014. 70 p.
Keyword
lone pairs, oxofluorides, low-dimensional compounds
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-103051 (URN)978-91-7447-890-7 (ISBN)
Public defence
2014-06-16, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 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 4: Manuscript. Paper 5: Manuscript.

Available from: 2014-05-22 Created: 2014-04-29 Last updated: 2014-08-29Bibliographically approved

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