期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 2013, 期 25, 页码 4410-4420出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201300373
关键词
Ruthenium; Polypyridyl ligands; Non-innocent ligands; EPR spectroscopy; Electrochemistry
资金
- UMass Boston
- Fonds der chemischen Industrie (FCI)
The electronic structure of [Ru(bpy)(2)(OQN)](+) (where bpy = 2,2-bipyridine and OQN = 8-oxyquinolate) has been revisited using a complimentary suite of theoretical (DFT/TD-DFT), electrochemical (cyclic voltammetry) and spectroscopic techniques (UV/Vis/NIR absorption, EPR spectroscopy). Through functionalization of the R-OQN ligand (R = 2-Me; 5,7-Me-2; 5-F; 5-Cl; 5,7-Cl-2; 5-NO2) charge delocalization across the non-innocent ruthenium-oxyquinolate framework has been investigated and correlated with substituent Hammett parameters. Combined spectroscopic and computational studies indicate substantial mixing at the HOMO-3, HOMO and LUMO+2 levels between the Ru and R-OQN -systems allowing controlled tuning of complex redox potentials while maintaining panchromatic absorption characteristics. UV/Vis/NIR and EPR spectroelectrochemical data is reported which shows strong evidence for substituent dependence of hole delocalization onto the R-OQN ligand following one-electron oxidation of the hybrid Ru(R-OQN) based HOMO level. EPR data correlates very well with Mulliken spin-density calculations confirming non-innocence of the R-OQN ligand which allows control of spin-distribution across the Ru(R-OQN) -system
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据