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KAKEN_25620066seika.pdf
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Title |
スピロ共役した不対電子間相互作用を活用した高次元スピンネットワークの構築
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Kana |
スピロ キョウヤクシタ フツイ デンシカン ソウゴ サヨウ オ カツヨウシタ コウジゲン スピン ネットワーク ノ コウチク
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Supiro kyoyakushita futsui denshikan sogo sayo o katsuyoshita kojigen supin nettowaku no kochiku
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Construction of high dimensional magnetic network by using spiro-conjugated unpaired electrons
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吉岡, 直樹
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ヨシオカ, ナオキ
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Yoshioka, Naoki
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慶應義塾大学・理工学部・教授
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Research team head
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科研費研究者番号 : 30222392
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2016
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科学研究費補助金研究成果報告書
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2015
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有機物からなる強磁性体の開発は, 機能材料の出現につながる重要な研究課題である。空間的に分子の広がりを持つ開殻分子を設計するために, スピロ共役型分子に着目し, 基礎的知見を整理することを目的とした。具体的には, 放射状に広がった系の中心構造としてスピロ共役を介した軌道間相互作用に基づき強磁性的なスピン整列が期待されるビアクリジン構造を, また複数のフェニル環を有する窒素中心型安定有機ラジカルを選択した。これらを効率よく合成するために, ラジカル状態で分子を化学修飾する方法を開拓した。さらにヘテロ原子を含むスピン原子を介した軌道間相互作用により, 強磁性的にスピン整列することを計算化学的に明らかにした。
To design open-shell molecules having a high dimensional magnetic network, synthesis and characterization of biacridine derivatives with hetero spiro atom and chemical modification of nitrogen centered stable organic radicals have been investigated. The physicochemical properties of spirobiacridine dinitroxide derivatives connected by Si or Ge spiro atom were studied. Their molecular and crystal structures were elucidated and their electronic states were evaluated by the spectroscopic methods. Their electronic structures and magnetic interaction were analyzed by the computational method and magnetic measurements. While ground triplet state was implied by the computational method, predominant antiferromagnetic interaction was observed due to the intermolecular close contact between spin centers. The chemical modification of nitrogen centered radicals such as verdazyl and triazynyl derivatives could be successfully conducted by the Suzuki-Miyaura cross-coupling reaction.
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研究種目 : 挑戦的萌芽研究
研究期間 : 2013~2015
課題番号 : 25620066
研究分野 : 有機機能材料化学
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