Spectroscopic and magnetic properties of FeOCl intercalated with organosulfur electron donors

Journal Article · Wed Jul 22 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00249a019· OSTI ID:6291691

Kauzlarich, S M; Ellena, J F; Stupik, P D; Reiff, W M; Averill, B A

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), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360603 -- Materials-- Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CARBON 15
CARBON ISOTOPES
CHLORINE COMPOUNDS
CLATHRATES
COHERENT SCATTERING
DATA
DIFFRACTION
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
GAMMA SPECTROMETERS
HALOGEN COMPOUNDS
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
IRON COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MATERIALS
MEASURING INSTRUMENTS
MOESSBAUER EFFECT
MOESSBAUER SPECTROMETERS
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYCHLORIDES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
POWDERS
RADIOISOTOPES
RESONANCE
SCATTERING
SECONDS LIVING RADIOISOTOPES
SEMICONDUCTOR MATERIALS
SPECTRA
SPECTROMETERS
SPECTROSCOPY
STABLE ISOTOPES
SUPERCONDUCTORS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION