在分子框架中具有同类的临界行为Zn () (CN) 2和Cd () (imidazolate) 2
Ines E Collings1, Andrew B Cairns, Amber L Thompson
1Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, United Kingdom.
(II) 化物和 (II) 伊米达酸盐中的结构扭曲揭示了对负热膨胀的见解. 这些发现表明,分子框架热力学取决于包装效率和动态不稳定性.
科学领域:
- 材料科学 材料科学 材料科学
- 固态化学 固态化学
- 晶体学 晶体学是指结晶学.
背景情况:
- 诸如 (Zn) 化物 (CN) 和 (II) 胺酸盐 (Cd) 等分子框架表现出复杂的结构行为.
- 了解它们对外部刺激的反应对于设计先进材料至关重要.
研究的目的:
- 研究Zn (CN) 2和Cd (im) 2.的温度和压力诱导的结构相变.
- 阐明Zn (CN) 中负热膨胀背后的原子机制2.
- 探索框架拓,包装效率和热力学特性之间的关系.
主要方法:
- 采用单晶和粉末X射线衍射测量方法.
- 进行了可变温度和可变压力研究.
- 进行了对原子位移和结构扭曲的分析.
主要成果:
- Zn(CN) 2 经历一等位移相转向 1.52 GPa 的正方形相.
- 原子位移涉及Zn中心四面体的相关倾斜,解释了负热膨胀.
- Cd(im) 2对温度变化表现出类似的机械反应,就像在压力下观察到的Zn(CN) 2一样.
结论:
- 该研究揭示了与负热膨胀相关的Zn(CN) 2中压力诱导的相位过渡.
- Zn(CN) 2和Cd(im) 2的机械行为表明了共同的热力学调节原理.
- 包装效率和动态框架不稳定性是分子框架热力学中的关键因素.
更多相关视频
09:22Synthesis and Performance Evaluations of ZnCoS/ZnCdS with Twin Crystal Structure for Multifunctional Redox Photocatalysis in Energy Applications
Published on: July 25, 2025
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
相关概念视频
Stereoisomerism
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Structural Isomerism
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 be...
Coordination Number and Geometry
Crystal Field Theory - Octahedral Complexes
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...
Valence Bond Theory
Crystal Field Theory - Tetrahedral and Square Planar 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,...
