The triruthenium complex [[(acac)2Ru(II)]3(L)] containing a conjugated diquinoxaline[2,3-a:2',3'-c]phenazine (L) bridge and acetylacetonate (acac) as ancillary ligands. Synthesis, spectroelectrochemical and EPR investigation.
The triruthenium complex [[(acac)2Ru(II)]3(L)] containing a conjugated diquinoxaline[2,3-a:2',3'-c]phenazine (L) bridge and acetylacetonate (acac) as ancillary ligands. Synthesis, spectroelectrochemical and EPR investigation.
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含有共轭二喹喔啉[2,3-a:2,3-c]吩嗪 (L) 桥和乙酰丙酮 (acac) 作为辅助配体的三钌配合物 [[(acac)2Ru(II)]3(L)]
DOI：
10.1039/b316007f
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发表时间：
2004
影响因子：
4
通讯作者：
G. K. Lahiri
中科院分区：
文献类型：
--
作者：
S. Patra;B. Sarkar;Sandeep Ghumaan;J. Fiedler;W. Kaim;G. K. Lahiri
化合物[[（acac）2 Ru]3（L）]（1）经历了三个独立的单电子氧化和还原过程。EPR的结果表明，从钌（II）中心的氧化和占领的一个主要是L-为基础的分子轨道上减少电子去除。尽管氧化分离良好（Δ E>或= 340 mV），但在维斯、NIR或IR区域中没有检测到明显的价间电荷转移带，表明混合价中间体1+和1（2+）中金属中心之间的电子耦合非常弱。分离的（Δ E>或= 540 mV）逐步还原产生与L的部分占据π * 轨道相关的弱近红外特征，1-的EPR谱中异常高的g各向异性归因于未成对电子占据简并MO。
The compound [[(acac)2Ru]3(L)] (1) undergoes three well-separated one-electron oxidation and reduction processes. The EPR results indicate electron removal from the ruthenium(II) centres on oxidation and the occupation of a largely L-based molecular orbital on reduction. In spite of well-separated (DeltaE > or = 340 mV) oxidation no obvious intervalence charge transfer bands were detected in the Vis, NIR or IR regions, suggesting very weak electronic coupling between the metal centres in the mixed-valent intermediates 1+ and 1(2+). The separated (DeltaE > or = 540 mV) stepwise reduction produces weak near-infrared features associated with partially occupied pi* orbitals of L, the unusually high g anisotropy in the EPR spectrum of 1- is attributed to the occupation of a degenerate MO by the unpaired electron.