Proton Transfer and a Dielectric Phase Transition in the Molecular Conductor (HDABCO+)2(TCNQ)3
- 12 December 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (1), 291-294
- https://doi.org/10.1021/ja0377697
Abstract
One-dimensional dielectric (N···H···N)∞ hydrogen-bonding chains of monoprotonated 1,4-diazabicyclo[2.2.2]octane (HDABCO+) were introduced into an electrically conducting 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) salt as the countercation structure. Room-temperature electrical conductivity was ∼10-3 S cm-1, with a semiconductive behavior. The temperature-dependent dielectric constants of (HDABCO+)2(TCNQ)3 indicated a dielectric transition at 306 K. A large deuterium isotope effect for the dielectric transition (ΔT = 70 K) was observed for the deuterated salt, (DDABCO+)2(TCNQ)3. Thermally activated order/disorder of the protons or deuteriums within the one-dimensional hydrogen-bonding chains of (HDABCO+)∞ and (DDABCO+)∞ affected the dielectric responses in the TCNQ-based semiconductors.Keywords
This publication has 21 references indexed in Scilit:
- Why Are There so Few Magnetic Ferroelectrics?The Journal of Physical Chemistry B, 2000
- Ferroelectricity inHydrogen Bonded CrystalsPhysical Review Letters, 1999
- Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2′-Bi-1H-imidazole System. II. Crystal Structures and Charge-Transfer Complex FormationsBulletin of the Chemical Society of Japan, 1996
- Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2′-Bi-1H-imidazole System. I. Acid Dissociation Constants and Redox Properties in SolutionBulletin of the Chemical Society of Japan, 1995
- 1 3C high resolution nuclear magnetic resonance studies in polycrystalline tetracyanoquinodimethaneThe Journal of Chemical Physics, 1992
- A Raman and infrared spectroscopic study of triethylenediamine (DABCO) and its protonated formsCanadian Journal of Chemistry, 1988
- Negative evidence for a proton-tunneling mechanism in the phase transition of-type crystalsPhysical Review B, 1987
- Hydrogen bonding and properties of organic conductors. 2. Electronic properties and structure of M2(TCNQ)3 and M(TCNQ)2 systemsThe Journal of Physical Chemistry, 1985
- The Intermolecular Interaction of Tetrathiafulvalene and Bis(ethylenedithio)tetrathiafulvalene in Organic Metals. Calculation of Orbital Overlaps and Models of Energy-band StructuresBulletin of the Chemical Society of Japan, 1984
- Optical properties of the radical cation tetrathiafulvalenium (TT) in its mixed-valence and monovalence halide saltsPhysical Review B, 1979