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Terminating species and Lewis acid-base preference in oxohalides – a new route to low-dimensional compounds
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based upon synthesis and structure determination of new transition metal oxo-halide compounds, which includes p-element cations that have a stereochemically active lone pair. A synthesis concept has been developed, which uses several different structural features to increase the possibility to yield a low-dimensional arrangement of transition metal cations. A total of 17 new compounds has been synthesised and their structures have been determined via single-crystal X-ray diffraction. The halides and the stereochemically active lone-pairs will typically act as terminating species segregating into regions of non-bonding volumes, which may take the form of 2D layers, 1D channels or Euclidean spheres. The transition metals that have been used for this work are copper, cobalt and iron. The Hard-Soft-Acid-Base principle has been utilized to match strong Lewis acids to strong Lewis bases and weak acids to weak bases. All compounds show tendencies towards low-dimensionality; they all have sheets of transition metal cations arranged into layers, where the layers most often are connected via weak dispersion forces.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi , 2007. , 174 p.
Keyword [en]
Low dimensionality, crystal structures, tellurites, selenites, oxohalides
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-1414ISBN: 91-7155-365-7 (print)OAI: oai:DiVA.org:su-1414DiVA: diva2:190063
Public defence
2007-02-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Opponent
Supervisors
Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
List of papers
1. Crystal Structure, magnetic properties and ionic conductivity of CuSbTeO3Cl2
Open this publication in new window or tab >>Crystal Structure, magnetic properties and ionic conductivity of CuSbTeO3Cl2
2003 In: Solid State Sciences, ISSN 1293-2558, Vol. 5, no 11-12, 1411-1416 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23082 (URN)
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
2. Crystal Structure of Cu3Bi(TeO3)2O2Cl: a Kagomé lattice type compound
Open this publication in new window or tab >>Crystal Structure of Cu3Bi(TeO3)2O2Cl: a Kagomé lattice type compound
2005 In: Solid State Sciences, ISSN 1293-2558, Vol. 7, no 4, 375-380 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23083 (URN)
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
3. Crystal Structure and magnetic properties of Cu3(TeO3)2Br2 – a layered compound with a new Cu(II) coordination polyhedron
Open this publication in new window or tab >>Crystal Structure and magnetic properties of Cu3(TeO3)2Br2 – a layered compound with a new Cu(II) coordination polyhedron
2006 In: Journal of Solid State Chemistry, ISSN 0022-4596, Vol. 178, no 6, 2024-2029 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23084 (URN)
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
4. Crystal Structure and Magnetic Properties of Co2TeO3Cl2 and Co2TeO3Br2
Open this publication in new window or tab >>Crystal Structure and Magnetic Properties of Co2TeO3Cl2 and Co2TeO3Br2
Show others...
2006 In: Journal of Solid State Chemistry, ISSN 0022-4596, Vol. 179, no 3, 836-842 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23085 (URN)
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
5. Crystal structure and magnetic properties of Co7(TeO3)4Br6 – a new cobalt tellurite bromide
Open this publication in new window or tab >>Crystal structure and magnetic properties of Co7(TeO3)4Br6 – a new cobalt tellurite bromide
Show others...
2006 In: Solid State Sciences, ISSN 1293-2558, Vol. 8, no 7, 836-842 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23086 (URN)
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
6. Crystal structure and magnetic properties of FeTe2O5X (X = Cl, Br) – a frustrated spin cluster compound with a new Te(IV) coordination polyhedron
Open this publication in new window or tab >>Crystal structure and magnetic properties of FeTe2O5X (X = Cl, Br) – a frustrated spin cluster compound with a new Te(IV) coordination polyhedron
Show others...
2006 In: Journal of the American Chemical Society, ISSN 0002-7863, Vol. 128, 15469-15475 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23087 (URN)
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
7. Monoclinic Cu3(SeO3)2Cl2: an oxohalide with an unusual CuO4Cl trigonal bipyramidal coordination
Open this publication in new window or tab >>Monoclinic Cu3(SeO3)2Cl2: an oxohalide with an unusual CuO4Cl trigonal bipyramidal coordination
2007 In: Acta Crystallographica Section C: Crystal Structure Communications, ISSN 0108-2701, Vol. C63, no 1, i4-i6 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23088 (URN)000243278800002 ()
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved
8. Crystal structure and magnetic properties of the new cobalt tellurite halide Co5(TeO3)4X2 (X = Cl, Br)
Open this publication in new window or tab >>Crystal structure and magnetic properties of the new cobalt tellurite halide Co5(TeO3)4X2 (X = Cl, Br)
Show others...
2007 (English)In: Solid State Sciences, ISSN 1293-2558, Vol. 9, no 3-4, 223-230 p.Article in journal (Refereed) Published
Abstract [en]

Two new cobalt tellurite halides Co5(TeO3)4Cl2 and Co5(TeO3)4Br2 have been synthesized and found to be iso-structural with Ni5(TeO3)4X2 (X = Cl, Br). Co5(TeO3)4X2 crystallizes in the monoclinic system space group C2/c, and the Br-phase has the lattice parameters a = 20.440(1) Å, b = 5.2760(2) Å, c = 16.4710(7) Å, β = 124.790(5)°, and Z = 4. The crystal structures were solved from single-crystal X-ray data, R1 = 1.90 and 1.77, respectively, for the Cl- and Br-phases. The crystal structure is layered with only weak van der Waals' interactions in between the layers. The layers are built by large [Co5O16X2] groups consisting of five edge- and face-sharing Co-octahedra. Each group is connected to adjacent groups via corner sharing through common oxygen atoms as well as through [TeO3E] groups. Magnetic susceptibility measurements on oriented single crystals reveal pronounced anisotropy in a broad temperature range and clear signs of antiferromagnetic ordering at low temperatures. Anisotropic susceptibility of an iso-structural Ni-based compound was also studied and compared with the corresponding results of Co5(TeO3)4X2. Magnetic anisotropy is discussed in framework of single-ion anisotropy effects.

Keyword
Oxohalide; Lone-pair elements; Crystal structure determination; Antiferromagnetism; Magnetic susceptibility
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-23089 (URN)10.1016/j.solidstatesciences.2006.11.019 (DOI)000246444300001 ()
Note
Part of urn:nbn:se:su:diva-1414Available from: 2007-01-02 Created: 2007-01-02 Last updated: 2010-07-26Bibliographically approved
9. Crystal Structure of the New Cobalt Tellurite Chloride Co5Te4O11Cl4
Open this publication in new window or tab >>Crystal Structure of the New Cobalt Tellurite Chloride Co5Te4O11Cl4
2007 (English)In: Zeitschrift für Anorganische und Allgemeines Chemie, ISSN 0044-2313, E-ISSN 1521-3749, Vol. 633, no 3, 422-424 p.Article in journal (Refereed) Published
Abstract [en]

The crystal structure of the new compound Co5Te4O11Cl4 is described. It crystallizes in the triclinic system, space group P-1 with the unit cell parameters a = 822.26(8) pm, b = 1029.7(1) pm, c = 1031.1(1) pm, = 110.80(1)°, β = 97.950(9)°, = 98.260(9)° and Z = 2. The structure is layered along the bc–plane and built by [CoO5Cl], [CoO4Cl2] and [CoO4Cl] polyhedra sandwiched by [TeO3E] and [TeO4E] polyhedra. The layers can be regarded as infinite molecules without any net charge and only weak van der Waals forces connect them to each other. The halides and the lone-pair, E, of TeIV protrude from the layers.

Place, publisher, year, edition, pages
Weinheim: WILEY-VCH Verlag, 2007
Keyword
Oxohalides, Tellurites, Lone–pair elements, Crystal structure
National Category
Other Basic Medicine
Identifiers
urn:nbn:se:su:diva-23090 (URN)10.1002/zaac.200600336 (DOI)
Available from: 2007-01-02 Created: 2007-01-02 Last updated: 2011-05-23Bibliographically approved
10. Crystal structure and magnetic properties of two new cobalt selenite halides: Co5(SeO3)4X2 (X=Cl, Br)
Open this publication in new window or tab >>Crystal structure and magnetic properties of two new cobalt selenite halides: Co5(SeO3)4X2 (X=Cl, Br)
Show others...
2007 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 180, no 3, 1051-1059 p.Article in journal (Refereed) Published
Abstract [en]

Two new isostructural cobalt selenite halides Co5(SeO3)4Cl2 and Co5(SeO3)4Br2 have been synthesized. They crystallize in the triclinic system space group P−1 with the following lattice parameters for Co5(SeO3)4Cl2: a=6.4935(8) Å, b=7.7288(8) Å, c=7.7443(10) Å, α=66.051(11)°, β=73.610(11)°, γ=81.268(9)°, and Z=1. The crystal structures were solved from single-crystal X-ray data, R1=3.73 and 4.03 for Co5(SeO3)4Cl2 and Co5(SeO3)4Br2, respectively. The new compounds are isostructural to Ni5(SeO3)4Br2.

Magnetic susceptibility measurements on oriented single-crystalline samples show anisotropic response in a broad temperature range. The anisotropic susceptibility is quantitatively interpreted within the zero-field splitting schemes for Co2+ and Ni2+ ions. Sharp low-temperature susceptibility features, at TN=18 and 20 K for Co5(SeO3)4Cl2 and Co5(SeO3)4Br2, respectively, are ascribed to antiferromagnetic ordering in a minority magnetic subsystem. In isostructural Ni5(SeO3)4Br2 magnetically ordered subsystem represents a majority fraction (TN=46 K). Nevertheless, anisotropic susceptibility of Ni5(SeO3)4Br2 is dominated at low temperatures by a minority fraction, subject to single-ion anisotropy effects and increasing population of Sz=0 (singlet) ground state of octahedrally coordinated Ni2+.

Keyword
Oxo-halide, Lone-pair elements, Crystal structure determination, Magnetic susceptibility, Zero-field splitting, Single-ion anisotropy
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-23091 (URN)10.1016/j.jssc.2006.12.035 (DOI)
Available from: 2007-01-02 Created: 2007-01-02 Last updated: 2011-02-16Bibliographically approved
11. Three new tellurite halides with unusual Te4+ coordinations and iron honeycomb lattice variants
Open this publication in new window or tab >>Three new tellurite halides with unusual Te4+ coordinations and iron honeycomb lattice variants
2007 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 180, no 5, 1750-1758 p.Article in journal (Refereed) Published
Abstract [en]

The crystal structure of three new iron and copper-iron tellurite halides are presented; (I) Cu3Fe8Te12O32Cl10 that crystallizes in the orthorhombic space group Pmmn, (II) Fe8Te12O32Cl3Br3 that crystallizes in the monoclinic space group P21/c, and (III) Fe5(TeO3)6Cl2 that crystallizes in the triclinic space group P-1. The crystal structures were solved from single crystal X-ray diffraction data. All three compounds have layered crystal structures where the Fe atoms form variants of the honeycomb lattice. Highly unusual Te4+ coordination polyhedra are exemplified: [TeO3+1E], [TeO3XE], [TeO3+1XE], and [TeO3X2E] (X=halide ion, E=the lone–pair valence electrons). The crystal structures contain large non-bonding volumes occupied by the stereochemically active lone–pair electrons on Te4+.

Keyword
Crystal structure determination, Iron, Oxo-halide, Lone–pair elements, Tellurites
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-23092 (URN)10.1016/j.jssc.2007.03.013 (DOI)
Available from: 2007-01-02 Created: 2007-01-02 Last updated: 2011-02-24Bibliographically approved

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