在金属-有机框架水晶结构下面有什么? 新设计原则来自意想不到的行为
Mark D Allendorf1, Vitalie Stavila1, Matthew Witman1
1Chemistry, Combustion, and Materials Science Center, Sandia National Laboratories, Livermore, California 94551, United States.
Journal of the American Chemical Society
|April 27, 2021
概括
由于微妙的化学因素,金属有机框架 (MOF) 往往会表现出意想不到的行为,挑战刚性结构假设. 重新检查MOF文献是发现新的设计规则和理解复杂的结构属性关系的关键.
科学领域:
- 材料科学
- 化学学
- 纳米技术
背景情况:
- 金属有机框架 (MOF) 具有明确的结构属性关系,对于储能和催化等应用至关重要.
- 目前的MOF设计原则依赖于结晶构成和结构刚性的假设.
- 这种理想化的观点可能会忽略微妙的化学细微差别,导致偏离预期的行为.
研究的目的:
- 识别和分析偏离理想化结构模型的MOF的意外行为.
- 挑战MOF刚性的假设并探索微妙的化学因素的影响.
- 激发对现有的MOF设计规则的重新评估,并揭示新的结构-属性关系.
主要方法:
- 对已记录的MOF行为进行了全面的文献审查.
- 对从理想化晶体图表中偏离的案例研究进行分析.
- 对各种MOF的预测性质与观察行为进行比较分析.
主要成果:
- 在文献中经常观察到偏离理想化的MOF结构和特性.
- 微妙的化学方面,并没有被晶体刚性捕获,显著影响MOF行为.
- 连接器拓和金属协调虽然有用,但不足以完全解释所有MOF属性.
结论:
- MOF的理想化晶体结构并不总是反映它们的实际化学行为.
- 为了理解复杂和意想不到的MOF功能,需要偏离理想的表示.
- 需要对MOF文献进行更广泛的审查,以完善设计原则并发现新的结构-属性相关性.
相关概念视频
Crystal Field Theory - Octahedral Complexes
28.7K
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...
28.7K
Metallic Solids
19.8K
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....
19.8K
Ionic Crystal Structures
16.0K
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
16.0K
Crystal Field Theory - Tetrahedral and Square Planar Complexes
45.8K
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,...
45.8K
Valence Bond Theory
10.0K
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...
10.0K
Properties of Organometallic Compounds
1.3K
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
1.3K


