Enhancement of ionic conductivity in organic ionic plastic crystals by introducing racemic ammonium ions

Masaya Matsuki; Teppei Yamada; Shun Dekura; Hiroshi Kitagawa; Nobuo Kimizuka

doi:10.1246/cl.171181

Enhancement of ionic conductivity in organic ionic plastic crystals by introducing racemic ammonium ions

Masaya Matsuki, Teppei Yamada, Shun Dekura, Hiroshi Kitagawa, Nobuo Kimizuka

Applied Chemistry

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

9 Citations (Scopus)

Abstract

An organic ionic plastic crystal (OIPC) consisting of racemic N_1233'Tf₂N (1) (N_1233' = NR₁R₂R₃R₄, R₁ = Me, R₂ = Et, R₃ = n-propyl, R₄ = isopropyl, Tf₂N = bis(trifluorometha-nesulfonyl)imide) is developed. 1 displays three solid phases in addition to the high-temperature liquid phase, and two intermediate phases are assigned to OIPC by DSC, powder XRD and solid-state NMR measurements. Ionic conductivity of 1 showed increase from the low-temperature region, and diffusion of Tf₂N anions was confirmed even at -27°C by NMR spectroscopy. This behavior is distinct from that of symmetric N_1223'Tf₂N (2), which showed much lower ionic conductivity at low temperatures. The introduction of racemic ions in OIPCs weakens the net intermolecular interactions and it enhances molecular motion and accordingly the ionic conductivity.

Original language	English
Pages (from-to)	497-499
Number of pages	3
Journal	Chemistry Letters
Volume	47
Issue number	4
DOIs	https://doi.org/10.1246/cl.171181
Publication status	Published - 2018

All Science Journal Classification (ASJC) codes

Chemistry(all)

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10.1246/cl.171181

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@article{8453033e47e04a9b9cf1565722043bbd,

title = "Enhancement of ionic conductivity in organic ionic plastic crystals by introducing racemic ammonium ions",

abstract = "An organic ionic plastic crystal (OIPC) consisting of racemic N1233'Tf2N (1) (N1233' = NR1R2R3R4, R1 = Me, R2 = Et, R3 = n-propyl, R4 = isopropyl, Tf2N = bis(trifluorometha-nesulfonyl)imide) is developed. 1 displays three solid phases in addition to the high-temperature liquid phase, and two intermediate phases are assigned to OIPC by DSC, powder XRD and solid-state NMR measurements. Ionic conductivity of 1 showed increase from the low-temperature region, and diffusion of Tf2N anions was confirmed even at -27°C by NMR spectroscopy. This behavior is distinct from that of symmetric N1223'Tf2N (2), which showed much lower ionic conductivity at low temperatures. The introduction of racemic ions in OIPCs weakens the net intermolecular interactions and it enhances molecular motion and accordingly the ionic conductivity.",

author = "Masaya Matsuki and Teppei Yamada and Shun Dekura and Hiroshi Kitagawa and Nobuo Kimizuka",

note = "Funding Information: This work was partly supported by JST PRESTO Grant Number JPMJPR141D, Japan and JSPS KAKENHI Grant Numbers JP25220805, JP16H06513 (Coordination Asymmetry). We would like to show our appreciations to Dr. Tetsuya Matsumoto for VT-XRPD measurements. Publisher Copyright: {\textcopyright} 2018 The Chemical Society of Japan.",

year = "2018",

doi = "10.1246/cl.171181",

language = "English",

volume = "47",

pages = "497--499",

journal = "Chemistry Letters",

issn = "0366-7022",

publisher = "The Chemical Society of Japan",

number = "4",

}

TY - JOUR

T1 - Enhancement of ionic conductivity in organic ionic plastic crystals by introducing racemic ammonium ions

AU - Matsuki, Masaya

AU - Yamada, Teppei

AU - Dekura, Shun

AU - Kitagawa, Hiroshi

AU - Kimizuka, Nobuo

N1 - Funding Information: This work was partly supported by JST PRESTO Grant Number JPMJPR141D, Japan and JSPS KAKENHI Grant Numbers JP25220805, JP16H06513 (Coordination Asymmetry). We would like to show our appreciations to Dr. Tetsuya Matsumoto for VT-XRPD measurements. Publisher Copyright: © 2018 The Chemical Society of Japan.

PY - 2018

Y1 - 2018

N2 - An organic ionic plastic crystal (OIPC) consisting of racemic N1233'Tf2N (1) (N1233' = NR1R2R3R4, R1 = Me, R2 = Et, R3 = n-propyl, R4 = isopropyl, Tf2N = bis(trifluorometha-nesulfonyl)imide) is developed. 1 displays three solid phases in addition to the high-temperature liquid phase, and two intermediate phases are assigned to OIPC by DSC, powder XRD and solid-state NMR measurements. Ionic conductivity of 1 showed increase from the low-temperature region, and diffusion of Tf2N anions was confirmed even at -27°C by NMR spectroscopy. This behavior is distinct from that of symmetric N1223'Tf2N (2), which showed much lower ionic conductivity at low temperatures. The introduction of racemic ions in OIPCs weakens the net intermolecular interactions and it enhances molecular motion and accordingly the ionic conductivity.

AB - An organic ionic plastic crystal (OIPC) consisting of racemic N1233'Tf2N (1) (N1233' = NR1R2R3R4, R1 = Me, R2 = Et, R3 = n-propyl, R4 = isopropyl, Tf2N = bis(trifluorometha-nesulfonyl)imide) is developed. 1 displays three solid phases in addition to the high-temperature liquid phase, and two intermediate phases are assigned to OIPC by DSC, powder XRD and solid-state NMR measurements. Ionic conductivity of 1 showed increase from the low-temperature region, and diffusion of Tf2N anions was confirmed even at -27°C by NMR spectroscopy. This behavior is distinct from that of symmetric N1223'Tf2N (2), which showed much lower ionic conductivity at low temperatures. The introduction of racemic ions in OIPCs weakens the net intermolecular interactions and it enhances molecular motion and accordingly the ionic conductivity.

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VL - 47

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EP - 499

JO - Chemistry Letters

JF - Chemistry Letters

IS - 4

ER -

Enhancement of ionic conductivity in organic ionic plastic crystals by introducing racemic ammonium ions

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