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Synthesis and crystal structure of Fe6Ca2(SeO3)(9)Cl-4 - a porous oxohalide
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Inorganic and Structural Chemistry.
2013 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 42, no 22, 7859-7862 p.Article in journal (Refereed) Published
Abstract [en]

A porous oxohalide, Fe6Ca2(SeO3)(9)Cl-4, has been synthesized by solid state reactions using concentrated HCl as the Cl-source. It crystallizes in the hexagonal space group P6(3)/m with unit cell parameters a = 12.118(2) angstrom, c = 12.703(4) angstrom, Z = 2. The crystal structure is an open framework having one-dimensional channels extending along [001] that the chlorine atoms and lone pairs on Se4+ are facing. The channels in this framework structure are unusually large compared to other oxohalide compounds and also accessible to guest molecules. Water vapor sorption measurements show an uptake of 9 wt% at 293 K.

Place, publisher, year, edition, pages
2013. Vol. 42, no 22, 7859-7862 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-92278DOI: 10.1039/c3dt50952dISI: 000318943400006OAI: oai:DiVA.org:su-92278DiVA: diva2:638028
Note

AuthorCount:2;

Available from: 2013-07-25 Created: 2013-07-25 Last updated: 2017-12-06Bibliographically 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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