A stable metallic state of (TTPCOO)2NH4 with a mobile dopant

Terauchi, Takeshi; Sumi, Satoshi; Kobayashi, Yuka; Nakamura, Toshikazu; Furukawa, Ko; Misaki, Yohji

doi:10.1039/c4cc00678j

Cited by 4 publications

(5 citation statements)

References 21 publications

(8 reference statements)

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“…Quinhydrone, the p -benzoquinone–hydroquinone organic 1:1 cocrystal, exhibits a cooperative proton–electron transfer, based on the coupling of the charge-transfer interaction and H-bond dynamics between the two organic π-electron components. , However, high pressure (∼25 kbar) is required for the realization of the proton–electron transferred state, and thus a detailed investigation has not been achieved. In addition, several kinds of possible candidates were prepared; − however, such “dynamic” coupling phenomena between H-bond dynamics and electrons in the solid state have scarcely been observed to date. , …”

Section: Introductionmentioning

confidence: 99%

Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism: A Phase Transition Caused by Deuterium and Electron Transfer in a Hydrogen-Bonded Purely Organic Conductor Crystal

et al. 2014

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A hydrogen bond (H-bond) is one of the most fundamental and important noncovalent interactions in chemistry, biology, physics, and all other molecular sciences. Especially, the dynamics of a proton or a hydrogen atom in the H-bond has attracted increasing attention, because it plays a crucial role in (bio)chemical reactions and some physical properties, such as dielectricity and proton conductivity. Here we report unprecedented H-bond-dynamics-based switching of electrical conductivity and magnetism in a H-bonded purely organic conductor crystal, κ-D3(Cat-EDT-TTF)2 (abbreviated as κ-D). This novel crystal κ-D, a deuterated analogue of κ-H3(Cat-EDT-TTF)2 (abbreviated as κ-H), is composed only of a H-bonded molecular unit, in which two crystallographically equivalent catechol-fused ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a +0.5 charge are linked by a symmetric anionic [O···D···O](-1)-type strong H-bond. Although the deuterated and parent hydrogen systems, κ-D and κ-H, are isostructural paramagnetic semiconductors with a dimer-Mott-type electronic structure at room temperature (space group: C2/c), only κ-D undergoes a phase transition at 185 K, to change to a nonmagnetic insulator with a charge-ordered electronic structure (space group: P1). The X-ray crystal structure analysis demonstrates that this dramatic switching of the electronic structure and physical properties originates from deuterium transfer or displacement within the H-bond accompanied by electron transfer between the Cat-EDT-TTF π-systems, proving that the H-bonded deuterium dynamics and the conducting TTF π-electron are cooperatively coupled. Furthermore, the reason why this unique phase transition occurs only in κ-D is qualitatively discussed in terms of the H/D isotope effect on the H-bond geometry and potential energy curve.

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Section: Introductionmentioning

confidence: 99%

Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism: A Phase Transition Caused by Deuterium and Electron Transfer in a Hydrogen-Bonded Purely Organic Conductor Crystal

et al. 2014

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“…These peaks showed frequency depend‐ence and apparently originated from proton motion. This paper focuses on the electronic properties, so a detailed discussion of the proton motion will be presented elsewhere . Since the relaxation of molecular motion is rapidly suppressed as the temperature is decreased, the nuclear spin relaxation at low temperatures (i.e., below 100 K) is mainly caused by electron spins.…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis, chemical analysis, and fundamental properties of (TTPCOO) 2 NH 4 were described in a previous report . Since single crystals of (TTFCOO)NH 4 and (TTPCOO) 2 NH 4 cannot be obtained at present, we carried out both magnetic resonance measurements using powder samples.…”

Section: Methodsmentioning

confidence: 99%

“…This system reduces the electronic correlation and displays a variety of molecular arrangements (i.e., dimensionality) (Fig. (a)) .…”

Section: Introductionmentioning

confidence: 99%

“…Extended π‐systems such as the TTP skeleton are one conservative strategy of realizing a two‐dimensional (2D) metal, and the electrical conductivity of (TTPCOO) 2 NH 4 is very high (13 S cm –1 ), even for a pressed pellet sample . The temperature dependence of the resistivity of the pressed pellet sample was weak and deviated from an Arrhenius activation type of that.…”

Section: Introductionmentioning

confidence: 99%

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Microscopic evidence of a metallic state in the one-pot organic conductor ammonium tetrathiapentalene carboxylate

Nakamura

Furukawa

Terauchi

et al. 2015

Phys. Status Solidi RRL

Self Cite

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1H NMR (nuclear magnetic resonance) and high‐field ESR (electron spin resonance) measurements were carried out for self‐doped organic conductors in the ammonium tetrathiapentalene carboxylate (TTPCOO)2[(NH41+)1–x(NH30)x ] system. While the pristine TTPCOOH molecule is closed‐shell, self‐doped carriers are generated by substitution of the carboxyl proton by (NH30) and (NH41+), which can be regarded as a charge reservoir. The π‐extended system TTPCOO has a uniaxial g ‐tensor, indicating a 2D isotropic structure such as a herring‐bone‐like or parallel cross donor arrangement. The NMR‐relaxation rate indicated the Korringa relation in the temperature dependence, and the ESR linewidth followed the Elliot mechanism. Both of these observations provide supporting evidence for a stable metallic state. In this paper, we introduce self‐doped organic conductors as a branch of materials design, and emphasize that advanced magnetic resonance measurements are powerful tools for developing functional materials. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)

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Carrier generation and electronic properties of a single-component pure organic metal

et al. 2016

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Metallic conduction generally requires high carrier concentration and wide bandwidth derived from strong orbital interaction between atoms or molecules. These requisites are especially important in organic compounds because a molecule is fundamentally an insulator; only multi-component salts with strong intermolecular interaction-namely, only charge transfer complexes and conducting polymers-have demonstrated intrinsic metallic behaviour. Herein we report a single-component electroactive molecule, zwitterionic tetrathiafulvalene(TTF)-extended dicarboxylate radical (TED), exhibiting metallic conduction even at low temperatures. TED exhibits d.c. conductivities of 530 S cm at 300 K and 1,000 S cm at 50 K with copper-like electronic properties. Spectroscopic and theoretical investigations of the carrier-generation mechanism and the electronic states of this single molecular species reveal a unique electronic structure with a spin-density gradient in the extended TTF moieties that becomes, in itself, a metallic state.

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A stable metallic state of (TTPCOO)2NH4 with a mobile dopant

Cited by 4 publications

References 21 publications

Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism: A Phase Transition Caused by Deuterium and Electron Transfer in a Hydrogen-Bonded Purely Organic Conductor Crystal

Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism: A Phase Transition Caused by Deuterium and Electron Transfer in a Hydrogen-Bonded Purely Organic Conductor Crystal

Microscopic evidence of a metallic state in the one-pot organic conductor ammonium tetrathiapentalene carboxylate

Carrier generation and electronic properties of a single-component pure organic metal

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