超低濃度のBi23-ラジカルを希土カチオンで抑制する
Peng Zhang1, Rizwan Nabi2, Jakob K Staab2
1Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States.
Journal of the American Chemical Society
|April 12, 2023
まとめ
稀土-ジビスムスの複合体を合成しました 新種のBi2−3ラジカルも含まれています これらの分子はユニークな結合と磁性特性を発揮し,単一分子の磁気の研究を進めています.
科学分野:
- 有機金属化学
- 無機化学
- 材料科学
- マグネティズム
背景:
- 稀土元素とpブロック元素は,先進的な材料の開発に不可欠です.
- ディビスムートアニオンは,協調化学において比較的未知のリガンドである.
- シングル分子磁石 (SMM) は,磁気特性の特定の分子構造を必要とします.
研究 の 目的:
- ディビスマスの橋渡しによる新しい稀土複合体を合成し,特徴づけること.
- このユニークな RE-Bi システムの電子構造と結合を調査します
- これらの相互作用から生じる磁気特性,特に単一分子磁気性を探求する.
主な方法:
- ディビスマスの橋渡しの稀土複合体の2つのシリーズの合成: (Cp*2RE) 2:η2-Bi2) と [K(crypt-222) ][Cp*2RE) 2:η2-Bi2•) · 2THF.
- シングルクリスタルX線 difraktion,UV-vis/NIRスペクトル,およびSQUID磁気測定を用いた特徴付け.
- DFTとマルチコンフィギュレーションをはじめとする計算分析.
主要な成果:
- 二磁性Bi2−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
- Bi23-ラジカル・ブリッジド・コンプレックス (2-Tbと2-Dy) は,磁気ヒステレスによる単分子磁気行動を示す.
- 分析により,金属中心と有意な同位体および無位体交換カップリングを持つBi23-の π*基 SOMO が明らかになった.
結論:
- これらの発見は,第2行を超えて金属イオンを橋渡しする最初のpブロックラジカルを表しています.
- この研究では,ランタニド-ビスムートとビスムート-ビスムート結合の性質とその磁気通信への影響が明らかにされています.
- 合成された分子は単一分子の磁気と協調化学の研究を進めるための大きな可能性を秘めています.
関連する概念動画
01:07Radicals: Electronic Structure and Geometry
4.1K
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
4.1K
01:10Radical Reactivity: Steric Effects
1.9K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
Along with electronic...
1.9K
01:33Radical Reactivity: Intramolecular vs Intermolecular
1.8K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
1.8K
01:11Radical Reactivity: Overview
2.1K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.1K
03:02Colors and Magnetism
12.0K
Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
12.0K
00:47Radical Formation: Addition
1.7K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
1.7K