异金属Ni/Cd复合固体中的素依赖多样性和弱相互作用:结构和理论研究
Oksana V Nesterova1, Svitlana R Petrusenko2,3, Brian W Skelton4
1Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Molecules (Basel, Switzerland)
|November 25, 2023
概括
合成了三种新型异金属/协调化合物. 热力学因素决定了结构,使得复合体之间的可逆转变成为可能,这是由于低能量障碍造成的.
科学领域:
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
- 计算化学的计算化学
背景情况:
- 异金属协调化合物具有可调节的特性.
- 自组装是构建复杂无机结构的关键策略.
- 了解结构属性关系对于材料设计至关重要.
研究的目的:
- 合成新的异金属Ni/Cd协调化合物.
- 研究反离子和溶剂对框架形成的影响.
- 阐明电子结构和连接体替代机制.
主要方法:
- 一个合成的Ni/Cd协调化合物.
- 用于结构确定的X射线晶体学.
- 密度函数理论 (DFT),CASSCF,以及初始联体场理论 (AILFT) 用于电子结构计算.
- 分子中的原子量子理论 (QTAIM) 用于分析分子间相互作用.
- 高级计算方法用于研究连接体替代机制.
主要成果:
- 成功合成了三种新型的异金属Ni/Cd协调化合物:[Ni}3][CdCl4]∙3dmso (1),[Ni}2(dmf) 2][CdBr4] (2),和[Ni}32[CdI4[I]2 (3).
- 观察到一个或三个维的键框架的形成,取决于对抗离子和溶剂.
- 计算了关键的电子结构,并分析了非共价相互作用.
- 证明了热力学因素决定结构的决定,这是由于对连接体旋转和可逆转换的低能量障碍造成的.
结论:
- 反离子和溶剂的性质显著影响这些Ni/Cd协调化合物中键框架的维度.
- 由低能障碍驱动的热力学控制在复合物的结构结果和相互转换中起着至关重要的作用.
- 计算研究为电子特性和反应机制提供了深入的见解,有助于合理设计新型协调材料.
相关概念视频
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
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
02:37Metallic Solids
18.4K
Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
18.4K
02:58Crystal Field Theory - Octahedral Complexes
26.6K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
26.6K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
42.7K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
42.7K
01:09Complexation Equilibria: Factors Influencing Stability of Complexes
376
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
376