テトラシアニド・ブリッジされたディバナジウム複合体:強い反鉄磁気結合と強い鉄磁気結合の間のリドックス・スイッチング

Matthew P Shores¹, Jeffrey R Long

¹Department of Chemistry, University of California, Berkeley, California 94720-1460, USA.

Journal of the American Chemical Society

|April 4, 2002

まとめ

この研究は,新しい双核バナジウムシアン化物複合体の合成を詳細に説明しています. この複合体は独特の磁気特性を持ち,縮小時に反鉄磁気結合から鉄磁気結合に切り替わります.

科学分野:

無機化学無機化学とは
協調化化学について
マテリアルサイエンス材料科学

背景:

マクロサイクリックリガンドを持つバナジウム複合体は,調節可能な電子特性を提供します.
シアン酸リガンドは金属の中心を橋渡しし,磁気交換相互作用に影響を与えることができます.
混合バレンスのシステムの理解は,新しい磁気材料の開発に不可欠です.

研究の目的:

新しい双核バナジウムシアン化物複合体を合成し,特徴づけること.
複合体の中性および還元された形態における磁気結合を調査する.
シアン酸オリゴメリゼーションの構造的および電子的影響を調査する.

主な方法:

[(Me3tacn) V ((CF3SO3) 3) ]が,DMF中のLiCNと反応する.
結果となる二核複合体の構造的特徴.
磁気感受性の測定と電気化学的還元研究.

主要な成果:

[{Me3tacn) 2V2{CN) 4{mu-C4N4}]の形成で,平面のテトラシアン化物ブリッジを特徴としています.
強い反鉄磁気結合 (J = -112 cm-1) と中性複合体における S = 0 基底状態.
ミックスバレンスのアニオンに還元される[{Me3tacn) 2V2{CN) 4{mu-C4N4) ]1- 鉄磁気結合とS = 3/2基底状態で.

結論:

テトラシアニドリガンドは,バナジウム中心間の重要な磁気結合を促進します.
複合体は,リドックス操作時に切り替え可能な磁気基底状態を示しています.
この研究は,バナジウムベースの磁気材料の設計に関する洞察を提供します.

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