慶應義塾研究者情報データベース

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• Magneto-Structural Correlation in Organic Radical Crystals Containing Nitroxyl and Triazinyl Spin Centers

  Yoshioka N., Takii M., Miura Y., Advances in Organic Crystal Chemistry Comprehensive Reviews 2025 on Crystal Functions, 2025年01月

  　概要を見る

  Stable organic radicals have drawn attention as promising building blocks for multifunctional materials. In order to realize the tailored magnets based on molecular materials, it is necessary to investigate magneto-structural correlation of open-shell molecules. In the present chapter, we describe the magnetic property of dihydroquinoline N-oxyl-based radicals and benztriazynyl-based radicals to discuss the substituent effect on molecular packing and intermolecular magnetic interaction. Relatively large magnetic interactions were observed through π-π stacking for dihydroquinoline N-oxyl-based radicals. Spin transition behavior was demonstrated in benztriazynyl-based radical.

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• Ferromagnetic interaction observed in the crystal of 5-methoxy-2,2-diphenyl-1,2-dihydroquinoline N-oxyl

  Takii M., Miura Y., Yoshioka N.

  Chemical Physics Letters 889 2026年04月

  ISSN  00092614

  　概要を見る

  A novel purely organic radical, 5-methoxy-2,2-diphenyl-1,2-dihydroquinoline N -oxyl ( 2 ), has been synthesized and structurally characterized in order to examine the substituent effect on the known derivative, 2,2-diphenyl-1,2-dihydroquinoline N -oxyl ( 1 ). Based on SQUID measurement, 2 exhibited a ferromagnetic interaction obeying the Bleaney–Bowers equation with 2 J = +17 cm⁻¹. X-ray analysis revealed that the 5-methoxy substitution induces an offset π-stacking, resulting in ferromagnetic interactions.

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• Synthesis and magnetic properties of 2,2-diphenyl-1,2-dihydroquinoline N-oxyl carrying an ethynyl group at the 5-position

  Takii M., Nishiura F., Yao M., Inoue H., Miura Y., Yoshioka N.

  New Journal of Chemistry 50 （ 3 ） 1377 - 1384 2026年01月

  ISSN  11440546

  　概要を見る

  Two aromatic nitroxyl radical derivatives of 2,2-diphenyl-1,2-dihydroquinoline N-oxyl (1), namely, 5-[2-(trimethylsilyl)ethynyl]-2,2-diphenyl-1,2-dihydroquinoline N-oxyl (2) and 5-ethynyl-2,2-diphenyl-1,2-dihydroquinoline N-oxyl (3), were synthesized, and their magneto-structural correlation was described in connection with their assembled structures. Single-crystal XRD analysis of 3 revealed a hydrogen bond between the oxygen atom in the nitroxyl group and the terminal hydrogen atom of the ethynyl group with d<inf>O⋯(H)C</inf> = 3.099(5) Å. SQUID measurements revealed that 3 follows a 1D antiferromagnetic chain model with J = −10.4 cm⁻¹. In contrast, a slight increase in the χ<inf>M</inf>T value to 0.44 emu K mol⁻¹ was observed in 2, with a decreasing temperature indicating the presence of a weak intermolecular ferromagnetic interaction. These magnetic behaviors differ from that of the unsubstituted radical 1.

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• 応用化学実験Ｃ

  2026年度

• 理工学基礎実験

  2026年度