一个有四个Rh2 4+紧固件的calix[4]arene车
F Albert Cotton1, Peng Lei, Chun Lin
1Laboratory for Molecular Structure and Bonding, Department of Chemistry, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA. cotton@tamu.edu
Journal of the American Chemical Society
|February 5, 2004
概括
研究人员通过将calix[4]arenes与二金属单元连接,捕获分子或离子,组装出稳定的球状. 这些子表现出了显著的稳定性,并允许晶体内配体交换,展示了动态的宿主-客体化学.
科学领域:
- 超分子化学 超分子化学
- 协调化学 协调化学
- 材料科学 材料科学 材料科学
背景情况:
- 开发用于客体封装的分子.
- 使用卡力克斯[4]竞技场作为复杂架构的构建块.
- 在超分子组合中探索金属与金属结合的单元.
研究的目的:
- 为了合成和表征新的球状.
- 为了研究分子和离子客体的封装.
- 评估体复合体的稳定性和动态性质.
主要方法:
- 通过将calix[4]arenes与dirhodium单元连接起来,组装体.
- 使用X射线晶体学,NMR,IR和质谱学进行表征.
- 研究单晶体中轴联体交换的研究.
主要成果:
- 成功合成了带有被捕获的四甲基离子的四甲基碳复合体 (1b).
- 证明了高稳定性和动态的轴联体交换 (乙/水),而不会损失结晶性.
- 相关的二金属-素化合物与二和二摩单元的表征.
结论:
- 球状体可以从[4]体和二金属单元中坚固地构建.
- 车具有显著的稳定性和可调节的客户环境.
- 晶体内联体交换突出了动态超分子材料的潜力.
相关概念视频
Chair Conformation of Cyclohexane
The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this staggered...
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Criteria for Aromaticity and the Hückel 4n + 2 Rule
Like benzene, cyclobutadiene and cyclooctatetraene are cyclic compounds with alternate single and double bonds. However, their chemical behavior differs from benzene, as they are unstable and not aromatic. So, what are the structural characteristics of unsaturated compounds categorized as aromatic?
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.
Five-Membered Heterocyclic Aromatic Compounds: Overview
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom, respectively.
Frost Circles for Different Conjugated Systems
The inscribed polygon method is consistent with Hückel’s 4n + 2 rule and helps to learn whether the given cyclic compound is aromatic or not. The compound is stable and aromatic if every bonding molecular orbital (MO) is completely filled with a pair of electrons. However, if the non-bonding or antibonding orbitals are filled with electrons, the compound is unstable and not aromatic. Consider the Frost circle diagrams for cycloalkenes containing 4 to 8 carbons.
Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...


