Electronic Communication Across Diamagnetic Metal Bridges: A Homoleptic Gallium(III) Complex of a Redox-Active Diarylamido-Based Ligand and Its Oxidized Derivatives
作者:Brendan J. Liddle、Sarath Wanniarachchi、Jeewantha S. Hewage、Sergey V. Lindeman、Brian Bennett、James R. Gardinier
DOI:10.1021/ic301437f
日期:2012.12.3
Complexes with cations of the type [Ga(L)2]n+ where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido and n = 1, 2, 3 have been prepared and structurally characterized. The electronic properties of each were probed by electrochemical and spectroscopic means and were interpreted with the aid of density functional theory (DFT) calculations. The dication, best described as [Ga(L–)(L0)]2+, is a Robin-Day
[Ga(L) 2 ] n +型阳离子配合物,其中 L = 双(4-甲基-2-(1H-吡唑-1-基)苯基)酰胺和n = 1, 2, 3结构特征。每个的电子特性通过电化学和光谱手段探测,并在密度泛函理论 (DFT) 计算的帮助下进行解释。最好的描述为 [Ga(L – )(L 0 )] 2+ 的指示是 Robin-Day II 类混合价物质。因此,在 6390–6925 cm –1范围内的 NIR 光谱中发现了一个宽的、弱的、依赖于溶剂的间隔电荷转移 (IVCT) 带,取决于溶剂。能带形状分析以及 Hush 和 Marcus 关系的使用揭示了适度的电子耦合,H ab约为 200 cm –1,以及电子转移的大速率常数k et,在氧化还原活性之间的数量级为 10 10 s –1配体。二氧化配合物 [Ga(L 0 ) 2 ] 3+在其固态 X 带电子顺磁共振 (EPR) 光谱中在 5 K 处显示半场 Δ