パルス電子スピン共鳴分光法による高対称高スピン有機分子の電子構造

• 研究課題/領域番号: 12740324
• 研究種目: 奨励研究(A)
• 配分区分: 補助金
• 研究分野: 物理化学
• 研究機関: 大阪市立大学
• 研究代表者: 佐藤 和信 大阪市立大学, 大学院・理学研究科, 講師 (90264796)
• 研究期間 (年度): 2000 – 2001
• 研究課題ステータス: 完了 (2001年度)
• 配分額: 2,100千円 (直接経費: 2,100千円); 2001年度: 800千円 (直接経費: 800千円); 2000年度: 1,300千円 (直接経費: 1,300千円)
• キーワード: ESR / パルスESR / 電子スピンニューテーション / 高スピン有機分子 / デカサイクレン / 多価アニオン状態 / ヤーンテラー効果 / 微細構造 / 非局在型分子 / ジアントリルカルベン / シクロペンタンジイルビラジラル / ESRスペクトルシミュレーション / 微細構造定数

研究概要

3回対称軸をもつ高対称性有機磁性体モデルとして、非局在化型カルベンや比較的安定なニトレンを3個導入した高スピン有機分子(I、II)や高対称有機分子デカサイクレンのトリアニオン高スピン状態(III)をcw-ESR法及びパルスESR/二次元電子スピンニューテーション法を用いて明らかにした。分子I、IIは、いずれも前駆体となるジアゾ化合物、アジド化合物を有機ガラス溶媒中に希釈した無秩序配向試料をアルゴンイオンレーザーを用いた光分解により反応中間体である高スピン分子を発生し、ESRの測定を行った。二次完スピンニューテーション分光法によるスペクトルの分離・スピン多重度の同定を行った後、スペクトルシミュレーション法を用いて微細構造定数を高精度で決定した。微細構造定数の理論的考察から、高スピン分子の電子状態・分子構造を明らかにした。特に、IIのニトレン系分子ではこれまで文献で報告されている値が誤っていることを証明し、電子状態と分子構造を統一的に理解できる微細構造定数を決定すると共に、報告されている値を修正した。IIIは、アルカリ金属と中性分子との化学還元を行うことにより生成し、ESRの測定を行った。トリアニオンに由来する四重項状態のESRスペクトルを観測し、基底四重項状態であることを明らかにした。ESR及び密度汎関数法を用いた分子軌道計算の結果と総合的に考察することにより、デカイサイクレンのトリアニオン状態において、分子構造のヤーンテラー歪みによるエネルギーの安定化が大きくないことを示した。これは、従来のトリアニオンが基底二重項状態であるとする説を覆すものである。また、四重項状態の微細構造定数の理論的考察から、IIIのような非局在化した高対称性の四重項状態の微細構造定数を取り扱うためには、3つの不対電子が相互作用する3体問題を顕わに考慮する必要があることを指摘した。

研究成果

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