Black Current: Structure, Characterization, and Optoelectronic Properties of Ce3Cl3[MoO6]

The admixture of CeO2, Ce, CeCl3, and MoO3 with an excess of LiCl as flux in evacuated silica ampules leads to large black single crystals as well as a black microcrystalline powder of Ce3Cl3[MoO6] after tempering at 850 °C for three days. The title compound crystallizes in the hexagonal space group...

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Veröffentlicht in:Chemistry : a European journal Jg. 25; H. 33; S. 7921 - 7926
Hauptverfasser: Dorn, Katharina V., Blaschkowski, Björn, Bamberger, Heiko, van Slageren, Joris, Doll, Klaus, Claus, Ralf, Matsumoto, Yosuke, Takagi, Hidenori, Hartenbach, Ingo
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim Wiley Subscription Services, Inc 12.06.2019
Schlagworte:
Admixtures
Ampules
Cerium
Cerium oxides
Chemistry
Crystal structure
Crystals
density functional calculations
Diffuse reflectance spectroscopy
Energy gap
EPR spectroscopy
I.R. radiation
Ions
Irradiation
Lithium chloride
Molecular orbitals
Molybdenum
Molybdenum oxides
Molybdenum trioxide
optoelectronic properties
Optoelectronics
oxidomolybdates
Powder
Silica
Silicon dioxide
Single crystals
Spectroscopy
Structural analysis
Unit cell
ISSN:0947-6539, 1521-3765, 1521-3765
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Abstract The admixture of CeO2, Ce, CeCl3, and MoO3 with an excess of LiCl as flux in evacuated silica ampules leads to large black single crystals as well as a black microcrystalline powder of Ce3Cl3[MoO6] after tempering at 850 °C for three days. The title compound crystallizes in the hexagonal space group P63/m (a=934.93(4), c=538.86(2) pm) with two formula units per unit cell. The crystal structure consists of rather unusual trigonal‐prismatic [MoO6]6− units besides Ce3+ ions in a tetra‐capped trigonal‐prismatic coordination, formed by four Cl− and six O2− ions. The black color is related to an optical band gap of 1.35(2) eV, which was determined by diffuse reflectance spectroscopy and confirmed by theoretical calculations. The low band gap between the 4f1 state of cerium (HOMO) and the 5d0 state of molybdenum (LUMO) gave rise to the idea of electronic excitation between these two states by IR irradiation, creating a drop in the resistivity of the material, which was detected by appropriate measurements. Switchable black: The black compound Ce3Cl3[MoO6] was obtained through solid‐state reactions and comprises trigonal‐prismatic [MoO6]6− entities. The material shows notable spectroscopic properties regarding the dependency of its specific resistivity under irradiation with IR light (see figure).
AbstractList The admixture of CeO2, Ce, CeCl3, and MoO3 with an excess of LiCl as flux in evacuated silica ampules leads to large black single crystals as well as a black microcrystalline powder of Ce3Cl3[MoO6] after tempering at 850 °C for three days. The title compound crystallizes in the hexagonal space group P63/m (a=934.93(4), c=538.86(2) pm) with two formula units per unit cell. The crystal structure consists of rather unusual trigonal‐prismatic [MoO6]6− units besides Ce3+ ions in a tetra‐capped trigonal‐prismatic coordination, formed by four Cl− and six O2− ions. The black color is related to an optical band gap of 1.35(2) eV, which was determined by diffuse reflectance spectroscopy and confirmed by theoretical calculations. The low band gap between the 4f1 state of cerium (HOMO) and the 5d0 state of molybdenum (LUMO) gave rise to the idea of electronic excitation between these two states by IR irradiation, creating a drop in the resistivity of the material, which was detected by appropriate measurements.
The admixture of CeO2, Ce, CeCl3, and MoO3 with an excess of LiCl as flux in evacuated silica ampules leads to large black single crystals as well as a black microcrystalline powder of Ce3Cl3[MoO6] after tempering at 850 °C for three days. The title compound crystallizes in the hexagonal space group P63/m (a=934.93(4), c=538.86(2) pm) with two formula units per unit cell. The crystal structure consists of rather unusual trigonal‐prismatic [MoO6]6− units besides Ce3+ ions in a tetra‐capped trigonal‐prismatic coordination, formed by four Cl− and six O2− ions. The black color is related to an optical band gap of 1.35(2) eV, which was determined by diffuse reflectance spectroscopy and confirmed by theoretical calculations. The low band gap between the 4f1 state of cerium (HOMO) and the 5d0 state of molybdenum (LUMO) gave rise to the idea of electronic excitation between these two states by IR irradiation, creating a drop in the resistivity of the material, which was detected by appropriate measurements. Switchable black: The black compound Ce3Cl3[MoO6] was obtained through solid‐state reactions and comprises trigonal‐prismatic [MoO6]6− entities. The material shows notable spectroscopic properties regarding the dependency of its specific resistivity under irradiation with IR light (see figure).
The admixture of CeO2, Ce, CeCl3, and MoO3 with an excess of LiCl as flux in evacuated silica ampules leads to large black single crystals as well as a black microcrystalline powder of Ce3Cl3[MoO6] after tempering at 850 degrees C for three days. The title compound crystallizes in the hexagonal space group P6(3)/m (a=934.93(4), c=538.86(2) pm) with two formula units per unit cell. The crystal structure consists of rather unusual trigonal-prismatic [MoO6](6-) units besides Ce3+ ions in a tetra-capped trigonal-prismatic coordination, formed by four Cl- and six O2- ions. The black color is related to an optical band gap of 1.35(2) eV, which was determined by diffuse reflectance spectroscopy and confirmed by theoretical calculations. The low band gap between the 4f(1) state of cerium (HOMO) and the 5d(0) state of molybdenum (LUMO) gave rise to the idea of electronic excitation between these two states by IR irradiation, creating a drop in the resistivity of the material, which was detected by appropriate measurements.
Author Bamberger, Heiko
Hartenbach, Ingo
Takagi, Hidenori
van Slageren, Joris
Blaschkowski, Björn
Dorn, Katharina V.
Doll, Klaus
Claus, Ralf
Matsumoto, Yosuke
Author_xml – sequence: 1
  givenname: Katharina V.
  surname: Dorn
  fullname: Dorn, Katharina V.
  organization: Stockholm University
– sequence: 2
  givenname: Björn
  surname: Blaschkowski
  fullname: Blaschkowski, Björn
  organization: University of Stuttgart
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  givenname: Heiko
  surname: Bamberger
  fullname: Bamberger, Heiko
  organization: University of Stuttgart
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  givenname: Joris
  surname: van Slageren
  fullname: van Slageren, Joris
  organization: University of Stuttgart
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  givenname: Klaus
  surname: Doll
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  organization: University of Stuttgart
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  givenname: Ralf
  surname: Claus
  fullname: Claus, Ralf
  organization: Max-Planck-Institute for Solid-State Research
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  surname: Matsumoto
  fullname: Matsumoto, Yosuke
  organization: Max-Planck-Institute for Solid-State Research
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  givenname: Hidenori
  surname: Takagi
  fullname: Takagi, Hidenori
  organization: Max-Planck-Institute for Solid-State Research
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  givenname: Ingo
  orcidid: 0000-0003-2489-5200
  surname: Hartenbach
  fullname: Hartenbach, Ingo
  email: ingo.hartenbach@iac.uni-stuttgart.de
  organization: University of Stuttgart
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Snippet The admixture of CeO2, Ce, CeCl3, and MoO3 with an excess of LiCl as flux in evacuated silica ampules leads to large black single crystals as well as a black...
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StartPage 7921
SubjectTerms Admixtures
Ampules
Cerium
Cerium oxides
Chemistry
Crystal structure
Crystals
density functional calculations
Diffuse reflectance spectroscopy
Energy gap
EPR spectroscopy
I.R. radiation
Ions
Irradiation
Lithium chloride
Molecular orbitals
Molybdenum
Molybdenum oxides
Molybdenum trioxide
optoelectronic properties
Optoelectronics
oxidomolybdates
Powder
Silica
Silicon dioxide
Single crystals
Spectroscopy
Structural analysis
Unit cell
Title Black Current: Structure, Characterization, and Optoelectronic Properties of Ce3Cl3[MoO6]
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