Electronic communication across diamagnetic metal bridges: a homoleptic gallium(III) complex of a redox-active diarylamido-based ligand and its oxidized derivatives.
Electronic communication across diamagnetic metal bridges: a homoleptic gallium(III) complex of a redox-active diarylamido-based ligand and its oxidized derivatives.
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跨抗磁金属桥的电子通信：氧化还原活性二芳基酰胺基配体及其氧化衍生物的均配镓（III）络合物。
DOI：
10.1021/ic301437f
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发表时间：
2012
影响因子：
4.6
通讯作者：
Gardinier,JamesR
中科院分区：
文献类型：
--
作者：
Liddle,BrendanJ;Wanniarachchi,Sarath;Hewage,JeewanthaS;Lindeman,SergeyV;Bennett,Brian;Gardinier,JamesR
合成了[Ga（L）2]n+型配合物，其中L =二（4-甲基-2-（1H-吡唑-1-基）苯基）氨基，n = 1，2，3，并进行了结构表征。每个的电子性质进行了探测电化学和光谱手段，并与密度泛函理论（DFT）计算的帮助下进行解释。二价阳离子[Ga（L-）（L0）]2+是Robin-Day II类混合价态。因此，在NIR光谱中在6390-6925 cm-1范围内发现了宽的、弱的、溶剂依赖性的价间电荷转移（IVCT）带，这取决于溶剂。带形分析和使用的Hush和Marcus关系揭示了适度的电子耦合，Habof约200 cm-1，和一个大的速率常数，电子转移，ket，在1010 s-1的数量级之间的氧化还原活性配体。[Ga（L0）2]3+的X波段电子顺磁共振（EPR）谱在5 K时显示出半场ΔMs= 2跃迁，表明三重态是热布居的。DFT计算（M06/Def 2-SV（P））表明，单重态的能量比三重态低21.7 cm-1。
Complexes with cations of the type [Ga(L)2]n+where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido andn= 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 class II mixed-valence species. As such, a broad, weak, solvent-dependent intervalence charge transfer (IVCT) band was found in the NIR spectrum in the range 6390–6925 cm–1, depending on the solvent. Band shape analyses and the use of Hush and Marcus relations revealed a modest electronic coupling,Habof about 200 cm–1, and a large rate constant for electron transfer,ket, on the order of 1010s–1between redox active ligands. The dioxidized complex [Ga(L0)2]3+shows a half-field ΔMs= 2 transition in its solid-state X-band electron paramagnetic resonance (EPR) spectrum at 5 K, which indicates that the triplet state is thermally populated. DFT calculations (M06/Def2-SV(P)) suggest that the singlet state is 21.7 cm–1lower in energy than the triplet state.