We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2)...We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2);n=1,3[PF6]_(2);n=5,4[PF6]_(2)) by using a mononuclear complex[PY5Me_(2)Ru(μ-CN)][PF_(6)](1) as the precursor.All the three complexes have been fully characterized by including single-crystal X-ray diffraction analysis.The one-electron oxidation complexes 2^(3+),3^(3+) and 4^(3+) obtained in situ all show a MMCT absorption band in the visible range.The MMCT energy increases as the redox potential of the N-terminal fragments decreases,and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases,supported by the TDF/TDDFT calculations.展开更多
基金the National Science Foundation of China(21773243,21973095)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB20010200)for financial support。
文摘We have designed and synthesized a family of dinuclear cyanido-bridged complexes[PY5Me_(2)Ru(μ-CN)Ru(dppe)CpMe_(n)][PF_(6)]_(2) (PY5Me_(2)=2,6-bis (1,1-bis(2-pyridyl)ethyl) pyridine,Cp=cyclopentadienyl,n=0,2[PF6]_(2);n=1,3[PF6]_(2);n=5,4[PF6]_(2)) by using a mononuclear complex[PY5Me_(2)Ru(μ-CN)][PF_(6)](1) as the precursor.All the three complexes have been fully characterized by including single-crystal X-ray diffraction analysis.The one-electron oxidation complexes 2^(3+),3^(3+) and 4^(3+) obtained in situ all show a MMCT absorption band in the visible range.The MMCT energy increases as the redox potential of the N-terminal fragments decreases,and the redox potential decreases as the number of methyl groups on the cyclopentadiene of the cyanido-nitrogen coordinated Ru metal increases,supported by the TDF/TDDFT calculations.
