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Charge Delocalization in a Cyclometalated Bisruthenium Complex Bridged by a Noninnocent 1,2,4,5-Tetra(2-pyridyl)benzene Ligand
Yao, Chang-Jiang; Zhong, Yu-Wu; Yao, Jiannian
2011-10-05
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN0002-7863
Volume133Issue:39Pages:15697-15706
AbstractTwo ruthenium atoms are covalently connected to the para positions of a phenyl ring in 1,2,4,5-tetra (2-pyridyl)benzene (tpb) to form a linear Ru-tpb-Ru arrangement. This unique structure leads to appealing electronic properties for the biscyclometalated complex [(tpy)Ru(tpb)Ru(tpy)](2+), where tpy is 2,2';6',2 ''-terpyridine. It could be stepwise oxidized at substantially low potential (+0.12 and +0.55 V vs Ag/AgCl) and with a noticeably large comproportionation constant (1.94 x 10(7)). In addition to the routinely observed metal-to-ligand charge-transfer transitions, [(tpy)Ru(tpb)Ru(tpy)](2+) displays a separate and distinct absorption band at 805 nm with appreciable absorptivity (epsilon = 9000 M-1 cm(-1)). This band is assigned to the charge transition from the Ru-tpb-Ru motif to the pyridine rings of tpb with the aide of density functional theory (DFT) and time-dependent DFT calculations. Complex [(tpy)Ru(tpb)Ru(tpy)](2+) was precisely titrated with 1 equiv of cerium ammonium nitrate to produce [(tpy)Ru(tpb)Ru(tpy)](3+), which shows intense multiple NIR transitions. The electronic coupling parameters flab of individual NIR components are determined to be 5812, 4942, 4358, and 3560 cm(-1). DFT and TDDFT calculation were performed on [(tpy)Ru(tpb)Ru(tpy)](3+) to elucidate its electronic structure and spin density population and the nature of the observed NIR transitions. Electron paramagnetic resonance studies of [(tpy)Ru(tpb)Ru(tpy)](3+) exhibit a discernible rhombic signal with the isotropic g factor of < g > = 2.144. These results point to the strong orbital interaction of tpb with metal centers and that tpb behaves as a redox noninnocent bridging ligand in [(tpy)Ru(tpb)Ru(tpy)](2+). Complex [(tpy)Ru(tpb)Ru(tpy)](3+) is determined to be a Robin-Day class III system with full charge delocalization across the Ru-tpb-Ru motif.
DOI10.1021/ja205879y
Indexed BySCI ; IC
Language英语
WOS IDWOS:000295911500073
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:102[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/71850
Collection中国科学院化学研究所
Corresponding AuthorZhong, Yu-Wu
AffiliationChinese Acad Sci, Beijing Natl Lab Mol Sci, CAS Key Lab Photochem, Inst Chem, Beijing 100190, Peoples R China
Recommended Citation
GB/T 7714
Yao, Chang-Jiang,Zhong, Yu-Wu,Yao, Jiannian. Charge Delocalization in a Cyclometalated Bisruthenium Complex Bridged by a Noninnocent 1,2,4,5-Tetra(2-pyridyl)benzene Ligand[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2011,133(39):15697-15706.
APA Yao, Chang-Jiang,Zhong, Yu-Wu,&Yao, Jiannian.(2011).Charge Delocalization in a Cyclometalated Bisruthenium Complex Bridged by a Noninnocent 1,2,4,5-Tetra(2-pyridyl)benzene Ligand.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,133(39),15697-15706.
MLA Yao, Chang-Jiang,et al."Charge Delocalization in a Cyclometalated Bisruthenium Complex Bridged by a Noninnocent 1,2,4,5-Tetra(2-pyridyl)benzene Ligand".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133.39(2011):15697-15706.
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