高旋转S = 2 基态氨基四原基的氨基四原基
Andrzej Rajca1, Arnon Olankitwanit, Ying Wang
1Department of Chemistry, University of Nebraska , Lincoln, Nebraska 68588-0304, United States.
Journal of the American Chemical Society
|November 21, 2013
概括
氨基四基基体表现出稳定的五重基态,三重兴奋状态的能量显著更高. 这些基因在溶液中形成二元体,并通过原子抽象分解,产生四胺.
科学领域:
- 有机化学 有机化学
- 量子化学 是一个量子化学.
- 材料科学 材料科学 材料科学
背景情况:
- 氨基四原基是新的有机分子,在分子磁力学中具有潜在的应用.
- 了解它们的电子结构和稳定性对于它们的实际使用至关重要.
研究的目的:
- 为了研究基底和激发的旋转状态的amiyl tetraradicals与 tetraazanonacene脊柱.
- 为了确定这些四根基在溶液中的稳定性和分解途径.
主要方法:
- 在不同温度下对2-甲基四氨基 (2-MeTHF) 矩阵进行实验研究.
- 破碎对称密度函数理论 (DFT) 的计算.
- 用光谱分析识别分解产物.
主要成果:
- 四根基具有五重体 (S = 2) 基态,没有可检测的低旋转激发状态群体,高达 100 K.
- 三重五重奏的能量差距 (ΔE(TQ)) 大于0.3 kcal mol(-1),与DFT计算一致.
- 在133K的缩溶液中,四根基形成二极体,具有弱的抗铁磁合.
- 绝缘屏蔽的四根基在室温下半衰期为1小时,通过从溶剂中抽取原子,分解为四胺基.
结论:
- 在研究条件下,氨基四基基在他们的五重奏基本状态下是稳定的.
- 分化和溶剂介导的分解是影响四基基稳定的关键因素.
更多相关视频
08:01Rapid Scan Electron Paramagnetic Resonance Opens New Avenues for Imaging Physiologically Important Parameters In Vivo
Published on: September 26, 2016
8.8K
09:00Experimental Methods for Spin- and Angle-Resolved Photoemission Spectroscopy Combined with Polarization-Variable Laser
Published on: June 28, 2018
9.3K
相关概念视频
Valence Bond Theory
8.9K
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...
8.9K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)
1.5K
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
1.5K
Radical Reactivity: Overview
2.2K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.2K
Atomic Nuclei: Nuclear Spin
5.1K
All atomic particles possess an intrinsic angular momentum, or 'spin'. Electrons, protons, and neutrons each have a spin value of ½, although protons and neutrons in nuclei may have higher half-integer spins owing to energetic factors.
Atomic nuclei have a net nuclear spin, , which can have an integer or half-integer value. In atomic nuclei, the spins of protons are paired against each other but not with neutrons, and vice versa. Consequently, an even number of protons does not contribute...
Atomic nuclei have a net nuclear spin, , which can have an integer or half-integer value. In atomic nuclei, the spins of protons are paired against each other but not with neutrons, and vice versa. Consequently, an even number of protons does not contribute...
5.1K
The Pauli Exclusion Principle
51.7K
The arrangement of electrons in the orbitals of an atom is called its electron configuration. We describe an electron configuration with a symbol that contains three pieces of information:
51.7K
Atomic Nuclei: Nuclear Spin State Overview
1.9K
NMR-active nuclei have energy levels called 'spin states' that are associated with the orientations of their nuclear magnetic moments. In the absence of a magnetic field, the nuclear magnetic moments are randomly oriented, and the spin states are degenerate. When an external magnetic field is applied, the spin states have only 2 + 1 orientations available to them. A proton with = ½ has two available orientations. Similarly, for a quadrupolar nucleus with a nuclear spin value of one, the...
1.9K
