N-Alkylimidazol-5-yl-substituted Nitronyl Nitroxides 和它们的单核Cu (II) 复合物:合成,结构和磁性特性
Irina V Golomolzina1, Svyatoslav E Tolstikov1, Kristina A Smirnova1
1International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3a, 630090, Novosibirsk, Russian Federation.
Chemistry (Weinheim an der Bergstrasse, Germany)
|December 20, 2023
概括
新的尼尼尔氧化物连接物被合成并形成铜复合体. 连接体上基链长度的增加改变了晶体包装,消除了类似化合物中观察到的化学机械活性.
科学领域:
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
- 有机合成 有机合成
背景情况:
- 尼烯酸氧化物是有机基,在分子磁力学中具有应用.
- 带有基联体的铜 (II) 复合体可以表现出有趣的磁性和机械性质.
- 之前的研究表明,相关的铜-双-氧化) 复合体中具有化学机械活性.
研究的目的:
- 为了合成新的尼特罗尼尔氧化物配体,使用不同的基替代剂.
- 为了研究由此产生的铜(II) 异体复合物的结构和磁性特性.
- 探索连接体结构对化学机械活性的影响.
主要方法:
- 对于基氧化联体 (L^n-Pr,L^i-Pr,L^n-Bu) 的新型合成方法.
- 通过与Cu(hfac) 2. 2的反应形成单核异氨酸复合体[Cu(hfac) 2[L^R) 2].
- 用X射线晶体学来确定晶体结构和包装.
- 测量磁性属性的测量.
主要成果:
- 成功合成了三种新的氧化二氧化 (nitronyl) 配体.
- 获得了与已知的"跳跃"晶体相似的结构的单核异蛋白复合体.
- 观察到基替代剂大小 (R) 的增加会破坏晶体包装并消除化学机械活性.
- 确定了 [Cu(hfac) 2(L^n-Pr) 2 的两个多态.
- 发现的磁性属性对氧化和伊米达环之间的二面角敏感.
结论:
- 氧化联体上基替代物的大小显著影响铜 (II) 复合物的晶体结构和特性.
- 由于改变了晶体包装,更大的基团抑制了化学机械活性.
- 观察到的磁性行为可以通过连接体设计和晶体结构来调整.
相关概念视频
02:34Structural Isomerism
19.2K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
19.2K
03:02Colors and Magnetism
11.7K
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...
11.7K
01:261° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
3.3K
Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...
3.3K
01:371° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
3.8K
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
3.8K
02:42Valence Bond Theory
8.6K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
8.6K
01:19Diazonium Group Substitution: –OH and –H
2.8K
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
2.8K