Charge delocalization of 1,4-benzenedicyclometalated ruthenium: A comparison between tris-bidentate and bis-tridentate complexes

Long Zhen Sui; Wen Wen Yang; Chang Jiang Yao; Hai Yan Xie; Yu Wu Zhong

doi:10.1021/ic202295b

Charge delocalization of 1,4-benzenedicyclometalated ruthenium: A comparison between tris-bidentate and bis-tridentate complexes

Long Zhen Sui, Wen Wen Yang, Chang Jiang Yao, Hai Yan Xie, Yu Wu Zhong^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

36 Citations (Scopus)

Abstract

A dimetallic biscyclometalated ruthenium complex, [(bpy) ₂Ru(dpb)Ru(bpy) ₂] ²⁺ (bpy = 2,2′- bipyridine; dpb = 1,4-di-2-pyridylbenzene), with a tris-bidentate coordination mode has been prepared. The electronic properties of this complex were studied by electrochemical and spectroscopic analysis and DFT/TDDFT calculations on both rac and meso isomers. Complex [(bpy) ₂Ru(dpb)Ru(bpy) ₂] ²⁺ has a similar 1,4-benzenedicyclometalated ruthenium (Ru-phenyl-Ru) structural component with a previously reported bis-tridentate complex, [(tpy)Ru(tpb)Ru(tpy)] ²⁺ (tpy = 2,2′;6′,2″- terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru-phenyl-Ru array were investigated and compared by studying the corresponding one-electron-oxidized species, generated by chemical oxidation or electrochemical electrolysis, with DFT/TDDFT calculations and spectroscopic and EPR analysis. These studies indicate that both [(bpy) ₂Ru(dpb)Ru(bpy) ₂] ³⁺ and [(tpy)Ru(tpb)Ru(tpy)] ³⁺ are fully delocalized systems. However, the coordination mode of the metal component plays an important role in influencing their electronic properties.

Original language	English
Pages (from-to)	1590-1598
Number of pages	9
Journal	Inorganic Chemistry
Volume	51
Issue number	3
DOIs	https://doi.org/10.1021/ic202295b
Publication status	Published - 6 Feb 2012
Externally published	Yes

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@article{275f02aa5f2b431cbe7c2eaf9c042cb8,

title = "Charge delocalization of 1,4-benzenedicyclometalated ruthenium: A comparison between tris-bidentate and bis-tridentate complexes",

abstract = "A dimetallic biscyclometalated ruthenium complex, [(bpy) 2Ru(dpb)Ru(bpy) 2] 2+ (bpy = 2,2′- bipyridine; dpb = 1,4-di-2-pyridylbenzene), with a tris-bidentate coordination mode has been prepared. The electronic properties of this complex were studied by electrochemical and spectroscopic analysis and DFT/TDDFT calculations on both rac and meso isomers. Complex [(bpy) 2Ru(dpb)Ru(bpy) 2] 2+ has a similar 1,4-benzenedicyclometalated ruthenium (Ru-phenyl-Ru) structural component with a previously reported bis-tridentate complex, [(tpy)Ru(tpb)Ru(tpy)] 2+ (tpy = 2,2′;6′,2″- terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru-phenyl-Ru array were investigated and compared by studying the corresponding one-electron-oxidized species, generated by chemical oxidation or electrochemical electrolysis, with DFT/TDDFT calculations and spectroscopic and EPR analysis. These studies indicate that both [(bpy) 2Ru(dpb)Ru(bpy) 2] 3+ and [(tpy)Ru(tpb)Ru(tpy)] 3+ are fully delocalized systems. However, the coordination mode of the metal component plays an important role in influencing their electronic properties.",

author = "Sui, {Long Zhen} and Yang, {Wen Wen} and Yao, {Chang Jiang} and Xie, {Hai Yan} and Zhong, {Yu Wu}",

year = "2012",

month = feb,

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doi = "10.1021/ic202295b",

language = "English",

volume = "51",

pages = "1590--1598",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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T1 - Charge delocalization of 1,4-benzenedicyclometalated ruthenium

T2 - A comparison between tris-bidentate and bis-tridentate complexes

AU - Sui, Long Zhen

AU - Yang, Wen Wen

AU - Yao, Chang Jiang

AU - Xie, Hai Yan

AU - Zhong, Yu Wu

PY - 2012/2/6

Y1 - 2012/2/6

N2 - A dimetallic biscyclometalated ruthenium complex, [(bpy) 2Ru(dpb)Ru(bpy) 2] 2+ (bpy = 2,2′- bipyridine; dpb = 1,4-di-2-pyridylbenzene), with a tris-bidentate coordination mode has been prepared. The electronic properties of this complex were studied by electrochemical and spectroscopic analysis and DFT/TDDFT calculations on both rac and meso isomers. Complex [(bpy) 2Ru(dpb)Ru(bpy) 2] 2+ has a similar 1,4-benzenedicyclometalated ruthenium (Ru-phenyl-Ru) structural component with a previously reported bis-tridentate complex, [(tpy)Ru(tpb)Ru(tpy)] 2+ (tpy = 2,2′;6′,2″- terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru-phenyl-Ru array were investigated and compared by studying the corresponding one-electron-oxidized species, generated by chemical oxidation or electrochemical electrolysis, with DFT/TDDFT calculations and spectroscopic and EPR analysis. These studies indicate that both [(bpy) 2Ru(dpb)Ru(bpy) 2] 3+ and [(tpy)Ru(tpb)Ru(tpy)] 3+ are fully delocalized systems. However, the coordination mode of the metal component plays an important role in influencing their electronic properties.

AB - A dimetallic biscyclometalated ruthenium complex, [(bpy) 2Ru(dpb)Ru(bpy) 2] 2+ (bpy = 2,2′- bipyridine; dpb = 1,4-di-2-pyridylbenzene), with a tris-bidentate coordination mode has been prepared. The electronic properties of this complex were studied by electrochemical and spectroscopic analysis and DFT/TDDFT calculations on both rac and meso isomers. Complex [(bpy) 2Ru(dpb)Ru(bpy) 2] 2+ has a similar 1,4-benzenedicyclometalated ruthenium (Ru-phenyl-Ru) structural component with a previously reported bis-tridentate complex, [(tpy)Ru(tpb)Ru(tpy)] 2+ (tpy = 2,2′;6′,2″- terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru-phenyl-Ru array were investigated and compared by studying the corresponding one-electron-oxidized species, generated by chemical oxidation or electrochemical electrolysis, with DFT/TDDFT calculations and spectroscopic and EPR analysis. These studies indicate that both [(bpy) 2Ru(dpb)Ru(bpy) 2] 3+ and [(tpy)Ru(tpb)Ru(tpy)] 3+ are fully delocalized systems. However, the coordination mode of the metal component plays an important role in influencing their electronic properties.

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DO - 10.1021/ic202295b

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SN - 0020-1669

VL - 51

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

Charge delocalization of 1,4-benzenedicyclometalated ruthenium: A comparison between tris-bidentate and bis-tridentate complexes

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