Proton Transfer and a Dielectric Phase Transition in the Molecular Conductor (HDABCO+)2(TCNQ)3

Tomoyuki Akutagawa; Sadamu Takeda; Tatsuo Hasegawa; Takayoshi Nakamura

Proton Transfer and a Dielectric Phase Transition in the Molecular Conductor (HDABCO⁺)₂(TCNQ)₃

Tomoyuki Akutagawa, Sadamu Takeda, Tatsuo Hasegawa, Takayoshi Nakamura

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	291-294
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	126
Issue number	1
Publication status	Published - 2004 Jan 14
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Cite this

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title = "Proton Transfer and a Dielectric Phase Transition in the Molecular Conductor (HDABCO+)2(TCNQ)3",

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.",

author = "Tomoyuki Akutagawa and Sadamu Takeda and Tatsuo Hasegawa and Takayoshi Nakamura",

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T1 - Proton Transfer and a Dielectric Phase Transition in the Molecular Conductor (HDABCO+)2(TCNQ)3

AU - Akutagawa, Tomoyuki

AU - Takeda, Sadamu

AU - Hasegawa, Tatsuo

AU - Nakamura, Takayoshi

PY - 2004/1/14

Y1 - 2004/1/14

N2 - 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.

AB - 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.

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Proton Transfer and a Dielectric Phase Transition in the Molecular Conductor (HDABCO⁺)₂(TCNQ)₃

Abstract

ASJC Scopus subject areas

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