Solvothermal synthesis of a bimetallic thiometallate containing germanium in two oxidation states
- Department of Chemistry, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom)
A new layered germanium-antimony sulphide, [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}], has been prepared at 463 K under solvothermal conditions in the presence of ethylenediamine. The compound has been characterised by single-crystal X-ray diffraction, thermogravimetry, elemental analysis and reflectance spectroscopy. [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}] crystallises in the space group Pbca (a=13.3284(5), b=17.4801(6), c=18.5447(7) A). The structure consists of cyclic [GeSb{sub 2}S{sub 8}]{sup 6-} units that form chains which are cross-linked through Sb{sub 2}S{sub 2} rings to generate layers of stoichiometry [GeSb{sub 2}S{sub 6}]{sup 2-}, between which [Ge(en){sub 3}]{sup 2+} cations are located. [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}] contains germanium in both the divalent and tetravalent states. The optical band gap of 2.49(4) eV is in excellent agreement with the value expected on the basis of the correlation with the density of metal centres previously identified for thioantimonates, and is consistent with states at the top of the valence band being predominantly of sulphur 3p character. - Graphical abstract: [Ge(C{sub 2}N{sub 2}H{sub 8}){sub 3}][GeSb{sub 2}S{sub 6}] is a mixed valent germanium compound that contains [GeSb{sub 2}S{sub 8}]{sup 6-} units cross linked through Sb{sub 2}S{sub 2} units to generate layers. Highlights: Black-Right-Pointing-Pointer Preparation and structural characterisation of a new mixed-metal thiometallate. Black-Right-Pointing-Pointer Germanium present in two oxidation states. Black-Right-Pointing-Pointer Optical band gap of 2.49(4) eV. Black-Right-Pointing-Pointer Band gap conforms to a correlation between band gap and density of metal centres.
- OSTI ID:
- 21612807
- Journal Information:
- Journal of Solid State Chemistry, Vol. 184, Issue 12; Other Information: DOI: 10.1016/j.jssc.2011.09.032; PII: S0022-4596(11)00525-1; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTIMONY
DENSITY
EV RANGE
GERMANIUM
GERMANIUM COMPOUNDS
LAYERS
MONOCRYSTALS
OPTICAL PROPERTIES
ORTHORHOMBIC LATTICES
SPACE GROUPS
SPECTROSCOPY
SULFIDES
SULFUR
SYNTHESIS
THERMAL GRAVIMETRIC ANALYSIS
X-RAY DIFFRACTION
CHALCOGENIDES
CHEMICAL ANALYSIS
COHERENT SCATTERING
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
ELEMENTS
ENERGY RANGE
GRAVIMETRIC ANALYSIS
METALS
NONMETALS
PHYSICAL PROPERTIES
QUANTITATIVE CHEMICAL ANALYSIS
SCATTERING
SULFUR COMPOUNDS
SYMMETRY GROUPS
THERMAL ANALYSIS