在混合价值,双核 (II) -bis (2,2':6',2' -) 复合体中的电子合的定向控制
Andrew C Benniston1, Anthony Harriman, Peiyi Li
1Molecular Photonics Laboratory, School of Natural Sciences, University of Newcastle, Newcastle upon Tyne, NE1 7RU, U.K.
Journal of the American Chemical Society
|October 21, 2004
概括
研究人员研究了带有变量的复合体. 他们发现,较长的带通过改变分子几何学来削弱金属中心之间的电子合,从而影响电荷转移特性.
科学领域:
- 协调化学 协调化学
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
背景情况:
- 双核复合体与 bis ((2,2':6',2''-terpyridine) 连接体是研究电子转移的关键.
- 双单元为结构修改提供了一个平台,以调整电子通信.
研究的目的:
- 为了合成和表征双核 (((II) 复合物与可调节的双烯链接器.
- 为了研究链接器长度对电子合和电荷转移特性在混合价值状态的影响.
主要方法:
- 合成具有不同长度带的双核 (II) -bis (2,2':6',2''-胺) 复合体.
- 部分氧化产生混合价值物种的电化学方法.
- 频谱分析 (UV-Vis-NIR) 用于研究电荷转移过渡.
主要成果:
- 混合价值复合体在近红外区域表现出联体到金属和间隔电荷转移 (IVCT) 过渡.
- 电子合 (H) 随着带长度的增加而减少,正如Hush理论所预测的那样.
- 带的长度影响了环之间的扭转角度,调节了通过键的电子合.
结论:
- 连接带的长度有效地控制了中心之间的电子通信.
- 分子几何学,特别是扭转角度,在调解电子合中起着至关重要的作用.
- 热波动限制了对电子合器扭转角度效应的充分实现.
更多相关视频
相关概念视频
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.
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...
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...
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...


