相关实验视频

Updated: Nov 16, 2025

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Published on: February 10, 2023

[CuOR]²⁺核心的结构特征

V Mahesh Krishnan¹, Dimitar Y Shopov¹, Caitlin J Bouchey¹

¹Department of Chemistry, Washington University in St. Louis, One Brookings Hall, Campus Box 1134, St. Louis, Missouri 63130-4899, United States.

Journal of the American Chemical Society

|February 23, 2021

概括

研究人员使用特定的配体稳定了高度反应性的铜 (III) 复合物,从而进行了详细的表征. 这些稳定的铜 (III) 复合体表现出更长的寿命和更慢的质子-合电子转移率.

科学领域:

无机化学
有机金属化学
协调化学

背景情况:

高反应性铜 (III) 种通常是短暂的,难以分离和描述.
了解铜的电子和结构性质对于催化和生物无机化学至关重要.

研究的目的:

稳定和描述难以捉摸的正规铜 (III) 复合物.
研究连接体设计对铜 (III) 种稳定性和反应性的影响.
探索这些反应性中间体的详细光谱和晶体分析的潜力.

主要方法:

用氧基辅助连接物 ([CuOR]²⁺) 合成正式的铜 (III) 复合物.
支持性联体 (L^Y) 供体特征和辅助性联体基本性的调节.
使用核磁共振 (NMR) 光谱和X射线晶体学进行表征.

主要成果:

成功稳定典型的高反应性铜 (III) 芯.
通过NMR光谱和X射线结晶学首次对这些铜 (III) 复合体进行了表征.
在溶液中观察到增长的寿命和减缓的质子合电子转移 (PCET) 速率.
核磁共振光谱证实了单点 (S = 0) 的基本状态.
在X射线结构中发现了与理论计算一致的缩短的Cu-ligand键距离.

结论:

干调制为稳定反应性铜 (III) 复合物提供了一种可行的策略.
稳定铜 (III) 复合体为详细的机械研究提供了一个平台.
这些发现促进了对铜氧化还原化学及其催化作用的理解.

更多相关视频

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

Published on: June 9, 2023

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications

Synthesis of Core-shell Lanthanide-doped Upconversion Nanocrystals for Cellular Applications

Published on: November 10, 2017

相关概念视频

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

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...

Aromatic Hydrocarbon Cations: Structural Overview

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...

Crystal Field Theory - Tetrahedral and Square Planar Complexes

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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,...

Additional Subnuclear Structures

Additional Subnuclear Structures

The eukaryotic nucleus is a double membrane-bound organelle that contains nearly all of the cell’s genetic material in the form of chromosomes. It is rightly called the “brain” of the cell as it shoulders the responsibility of responding to various physiological processes, stress, altered metabolic conditions, and other cellular signals.
The nucleus contains many membrane-less subnuclear organelles or nuclear bodies, such as nucleoli, Cajal bodies, speckles,...

Additional Subnuclear Structures

Additional Subnuclear Structures

Network Covalent Solids

Network Covalent Solids

Network covalent solids contain a three-dimensional network of covalently bonded atoms as found in the crystal structures of nonmetals like diamond, graphite, silicon, and some covalent compounds, such as silicon dioxide (sand) and silicon carbide (carborundum, the abrasive on sandpaper). Many minerals have networks of covalent bonds.
To break or to melt a covalent network solid, covalent bonds must be broken. Because covalent bonds are relatively strong, covalent network solids are typically...