One-dimensional spin dynamics in a halogen-bridged mixed-valence palladium (II), (IV) complex studied by 1H NMR

Ryuichi Ikeda; Masaki Iida; Tetsuo Asaji; Ashutosh Ghosh; Masahiro Yamashita

doi:10.1016/0009-2614(93)89103-O

One-dimensional spin dynamics in a halogen-bridged mixed-valence palladium (II), (IV) complex studied by ¹H NMR

Ryuichi Ikeda, Masaki Iida, Tetsuo Asaji, Ashutosh Ghosh, Masahiro Yamashita

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

14 Citations (Scopus)

Abstract

The ¹H NMR spin-lattice relaxation time T₁ of [Pd(chxn)₂][PdBr₂(chxn)₂]Br₄ (chxn = 1R,2R-cyclohexanediamine) in the solid state was measured between 90 K and room temperature at Larmor frequencies of 10-60 MHz. The presence of thermally activated diffusive spins formed on paramagnetic Pd^III sites along the halogen-bridged 1D chain was revealed from the Larmor frequency dependence of T₁. The diffusion rates were estimated to be 2 × 10¹³, 9 × 10¹¹, and 6 × 10¹⁰ rad s^-1 at 303, 198 and 125 K, respectively. The rate observed around room temperature showed an Arrhenius-type temperature dependence with an activation energy of ≈1700 K. It is shown that the diffusive spin is delocalized over several Pd sites. The observed spin motion is attributable to the neutral soliton by referring to the electrical conductivity data.

Original language	English
Pages (from-to)	78-83
Number of pages	6
Journal	Chemical Physics Letters
Volume	210
Issue number	1-3
DOIs	https://doi.org/10.1016/0009-2614(93)89103-O
Publication status	Published - 1993 Jul 23
Externally published	Yes

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "One-dimensional spin dynamics in a halogen-bridged mixed-valence palladium (II), (IV) complex studied by 1H NMR",

abstract = "The 1H NMR spin-lattice relaxation time T1 of [Pd(chxn)2][PdBr2(chxn)2]Br4 (chxn = 1R,2R-cyclohexanediamine) in the solid state was measured between 90 K and room temperature at Larmor frequencies of 10-60 MHz. The presence of thermally activated diffusive spins formed on paramagnetic PdIII sites along the halogen-bridged 1D chain was revealed from the Larmor frequency dependence of T1. The diffusion rates were estimated to be 2 × 1013, 9 × 1011, and 6 × 1010 rad s-1 at 303, 198 and 125 K, respectively. The rate observed around room temperature showed an Arrhenius-type temperature dependence with an activation energy of ≈1700 K. It is shown that the diffusive spin is delocalized over several Pd sites. The observed spin motion is attributable to the neutral soliton by referring to the electrical conductivity data.",

author = "Ryuichi Ikeda and Masaki Iida and Tetsuo Asaji and Ashutosh Ghosh and Masahiro Yamashita",

year = "1993",

month = jul,

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doi = "10.1016/0009-2614(93)89103-O",

language = "English",

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journal = "Chemical Physics Letters",

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T1 - One-dimensional spin dynamics in a halogen-bridged mixed-valence palladium (II), (IV) complex studied by 1H NMR

AU - Ikeda, Ryuichi

AU - Iida, Masaki

AU - Asaji, Tetsuo

AU - Ghosh, Ashutosh

AU - Yamashita, Masahiro

PY - 1993/7/23

Y1 - 1993/7/23

N2 - The 1H NMR spin-lattice relaxation time T1 of [Pd(chxn)2][PdBr2(chxn)2]Br4 (chxn = 1R,2R-cyclohexanediamine) in the solid state was measured between 90 K and room temperature at Larmor frequencies of 10-60 MHz. The presence of thermally activated diffusive spins formed on paramagnetic PdIII sites along the halogen-bridged 1D chain was revealed from the Larmor frequency dependence of T1. The diffusion rates were estimated to be 2 × 1013, 9 × 1011, and 6 × 1010 rad s-1 at 303, 198 and 125 K, respectively. The rate observed around room temperature showed an Arrhenius-type temperature dependence with an activation energy of ≈1700 K. It is shown that the diffusive spin is delocalized over several Pd sites. The observed spin motion is attributable to the neutral soliton by referring to the electrical conductivity data.

AB - The 1H NMR spin-lattice relaxation time T1 of [Pd(chxn)2][PdBr2(chxn)2]Br4 (chxn = 1R,2R-cyclohexanediamine) in the solid state was measured between 90 K and room temperature at Larmor frequencies of 10-60 MHz. The presence of thermally activated diffusive spins formed on paramagnetic PdIII sites along the halogen-bridged 1D chain was revealed from the Larmor frequency dependence of T1. The diffusion rates were estimated to be 2 × 1013, 9 × 1011, and 6 × 1010 rad s-1 at 303, 198 and 125 K, respectively. The rate observed around room temperature showed an Arrhenius-type temperature dependence with an activation energy of ≈1700 K. It is shown that the diffusive spin is delocalized over several Pd sites. The observed spin motion is attributable to the neutral soliton by referring to the electrical conductivity data.

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