High-Resolution Solid-State NMR Investigation of the Phase Transition in Decamethylferrocene-Acenaphthenequinone Charge-Transfer Complex

Hideaki Nakamura; Daisuke Kuwahara; Tomoyuki Mochida

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High-Resolution Solid-State NMR Investigation of the Phase Transition in Decamethylferrocene-Acenaphthenequinone Charge-Transfer Complex

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A charge-transfer complex composed of decamethylferrocene (D) and acenaphthenequinone (A) was prepared.The material was a 1:1 neutral complex with a mixed-stack structure and exhibited a phase transition at -16 °C. High-resolution 13C and 1H NMR spectroscopy revealed that an inclination of A with respect to D occurs below the phase-transition temperature. The 1H spin-diffusion rates of the complex undergoing highspeed magic-angle spinning (MAS) were measured to determine the shortest 1H-1H distance r between D and A. To analyze the experimental results, we derived the analytical expression of the spin-diffusion rate Wz for a homonuclear multispin system undergoing MAS. It was found that Wz for the complex is proportional only to 1/r6 under high-speed MAS conditions. On the basis of this relationship and the crystal structure at 20 °C, it was determined that the shortest 1H-1H distance r at -27.7 °C (below the phase transition temperature) is 0.4 A shorter than that at 20 °C. Given this information, a plausible model of the low-temperature structure is discussed.

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2009年第48期|13601-13607|共7页
作者
Hideaki Nakamura; Daisuke Kuwahara; Tomoyuki Mochida;
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作者单位

Mitsubishi Materials Corporation, 5 Mitacho,Yokkaichi-shi, Mie 510-0841, Japan;

The UniVersity of Electro-Communications, 1-5-1 Chofugaoka, Chofu-shi, Tokyo 182-8585, Japan;

Department of Chemistry, Graduate School of Science, Kobe UniVersity, Rokkodai,Nada, Kobe 657-8501, Japan;

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正文语种英语
中图分类物理化学（理论化学）、化学物理学;
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High-Resolution; Investigation; Transition;

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High-Resolution Solid-State NMR Investigation of the Phase Transition in Decamethylferrocene-Acenaphthenequinone Charge-Transfer Complex

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