Hua Kai, Xie Fei, Ye Shengfa, Zhang Ming-Tian
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
JACS Au. 2024 Oct 16;4(11):4406-4414. doi: 10.1021/jacsau.4c00745. eCollection 2024 Nov 25.
In this report, we present a structurally and spectroscopically characterized diorganocopper system in three distinct oxidation states: [CuCu] (), [CuCu] (), and [CuCu] (). These states are stabilized by a macrocyclic ligand scaffold featuring two square-planar coordination {C N }. We have analyzed the geometric and electronic structures using X-ray diffraction (XRD) and multiple spectroscopic methods including nuclear magnetic resonance (NMR), UV-vis, and electron paramagnetic resonance (EPR) spectroscopies, in combination with density functional theory (DFT) calculations. Remarkably, this study provides a structural determination of mixed-valence diorganocopper(II,III) complex , which is at the borderline between valence-trapped or charge-localized class I systems and charge moderately delocalized class II systems in Robin and Day classification. These findings enhance our understanding of the systematic structural and electronic changes that occur in diorganocopper complexes in response to redox transformations.
在本报告中，我们展示了一种具有三种不同氧化态的结构和光谱特征明确的二有机铜体系：[CuCu]（）、[CuCu]（）和[CuCu]（）。这些状态由具有两个平面正方形配位{C N }的大环配体支架稳定。我们使用X射线衍射（XRD）和多种光谱方法，包括核磁共振（NMR）、紫外可见光谱（UV-vis）和电子顺磁共振（EPR）光谱，并结合密度泛函理论（DFT）计算，分析了其几何和电子结构。值得注意的是，本研究提供了混合价二有机铜（II,III）配合物的结构测定，该配合物处于罗宾和戴分类中价态捕获或电荷局域化的I类体系与电荷适度离域的II类体系之间的边界。这些发现加深了我们对二有机铜配合物中因氧化还原转变而发生的系统结构和电子变化的理解。
