三角形双金字塔协调中的Mn3+:一个新的蓝色染色体
Andrew E Smith1, Hiroshi Mizoguchi, Kris Delaney
1Department of Chemistry, Oregon State University, Corvallis, Oregon 97330-4003, USA.
Journal of the American Chemical Society
|November 11, 2009
概括
三价 (Mn3+) 在氧化物中产生鲜的蓝色. 这是由于其三角形双金字塔协调中的特定电子转换引起的,导致光吸收.
科学领域:
- 材料科学 材料科学 材料科学
- 固态化学 固态化学
- 固态物理 固态物理
背景情况:
- 氧化物的颜色通常是由过渡金属离子的电子结构决定的.
- 了解氧化物中颜色的起源可以导致新的材料设计.
研究的目的:
- 为了研究三价 (Mn3+) 在氧化物中赋予的强烈蓝色的起源.
- 阐明导致这种现象的电子和光学特性.
主要方法:
- 进行了光学测量来分析吸收光谱.
- 第一个原则密度函数理论 (DFT) 的计算被用来建模电子结构.
主要成果:
- 三价 (Mn3+) 在三角二协调中会导致氧化物中强烈的蓝色.
- 蓝色的颜色来自于光谱的红/绿区域的强烈吸收.
- 这种吸收归因于一个允许对称的光学过渡,涉及Mn 3d状态与O 2p状态混合.
结论:
- 观察到的蓝色是稀释Mn3+在这种特定的协调环境中的一般特征.
- 这些发现提供了对氧化物中颜色中心的基本理解,以及调整光学属性的潜力.
相关概念视频
Colors and Magnetism
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 eye.
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 eye.
Valence Bond Theory
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...
Coordination Number and Geometry
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
Structure of Amines
The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
Structural Isomerism
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 be...
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...
Stereoisomerism
Isomerism in Complexes
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...
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...


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