Spectroscopic and magnetic properties of FeOCl intercalated with organosulfur electron donors
In an effort to develop a new type of low-dimensional conductor, the intercalation chemistry of FeOCl with tetrathiolene molecules has been explored. New intercalation compounds of the organic electron donors TTF (tetrathiafulvalene), TMTTF (tetramethyltetrathiafulvalene), TTN (tetrathianaphthalene), and TTT (tetrathiatetracene) with the inorganic host FeOCl were prepared by direct reaction of solutions of the organosulfur compounds with solid FeOCl. The new phases obtained were FeOCl(TTF)/sub 1/8.5/, FeOCl(TMTTF)/sub 1/13/, FeOCl(TTN)/sub 1/9/(tol)/sub 1/22/, and FeOCl(TTT)/sub 1/9/ (tol)/sub 1/23/. X-ray powder diffraction data are consistent with the tetrathiolene molecule being oriented perpendicular to the layers, with the exception of FeOCl(TMTTF)/sub 1/13/, in which the TMTTF molecule is oriented parallel to the host layers. Detailed wideline /sup 1/H and cross polarization magic angle spinning (CPMAS) /sup 13/C NMR studies carried out on FeOCl(TTF)/sub 1/8.5/ and related model compounds indicate that there is more than one type of ordering of the TTF molecules characterized by different average TTF environments and/or dynamics. The pressed powder electrical conductivity of FeOCl intercalated with these tetrathiolenes is 10/sup 3/-10/sup 5/ times that of the pristine material (sigma/sub RT/FeOCl approx. 10/sup -7/ (Omega-cm)/sup -1/). The temperature dependence of the conductivity is consistent with FeOCl and the intercalates being semiconductors with apparent bandgaps of 0.6 eV and ca. 0.3-0.4 eV, respectively. Infrared spectra indicate that the tetrathiolene molecules exist as radical cations within the layers.
- Research Organization:
- Michigan State Univ., East Lansing
- OSTI ID:
- 6291691
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 109:15
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
CARBON 15
NMR SPECTRA
HYDROGEN 1
IRON COMPOUNDS
ABSORPTION SPECTROSCOPY
MOESSBAUER SPECTROMETERS
NUCLEAR MAGNETIC RESONANCE
ORGANIC SULFUR COMPOUNDS
OXYCHLORIDES
CLATHRATES
ELECTRIC CONDUCTIVITY
EXPERIMENTAL DATA
INFRARED SPECTRA
MOESSBAUER EFFECT
POWDERS
SEMICONDUCTOR MATERIALS
SUPERCONDUCTORS
X-RAY DIFFRACTION
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CARBON ISOTOPES
CHLORINE COMPOUNDS
COHERENT SCATTERING
DATA
DIFFRACTION
ELECTRICAL PROPERTIES
EVEN-ODD NUCLEI
GAMMA SPECTROMETERS
HALOGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MATERIALS
MEASURING INSTRUMENTS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
RADIOISOTOPES
RESONANCE
SCATTERING
SECONDS LIVING RADIOISOTOPES
SPECTRA
SPECTROMETERS
SPECTROSCOPY
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
360603 - Materials- Properties