Binuclear Ruthenium Complexes with Benzo[1, 2‐b;4, 5‐b′]dithiophene Analogues as Bridge Ligands: Syntheses, Characterization and Notable Difference on Electronic Coupling. Issue 7 (29th June 2017)

• Record Type: Journal Article
• Authors: Ou, Ya‐Ping; Tang, Shunlin; Wang, Aihui; Li, Junhua; Zhang, Fuxing; Xu, Zhifeng
• Is Part Of: Chinese journal of chemistry. Volume 35:Issue 7(2017)
• Page Start: 1170
• Page End: 1178
• Publication Date: 2017-06-29
• Subjects: bridge ligands -- ruthenium terminal groups -- spectroelectrochemistry -- electronic coupling; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cjoc.201700220
• Languages: English
• ISSNs: 1001-604X

Abstract

Abstract : Diruthenium ethynyl complexes1 –3 (1 : 1, 5‐dithia‐s‐indacene‐4, 8‐dione;2 : 4, 8‐diethoxybenzo[1, 2‐b:4, 5‐ b']dithiophene;3 : 4, 8‐didodecyloxybenzo[1, 2‐b:4, 5‐b']dithiophene) have been synthesized by incorporating the respective conjugated heterocyclic spacer and characterized by NMR and elemental analysis. The effects of bridge ligands' properties on electronic coupling between redox‐active ruthenium terminal groups were investigated by electrochemistry, UV/vis/near‐IR and IR spectroelectrochemistry combined with density functional theory (DFT) and time‐dependent DFT calculations. Electrochemistry results indicated that complexes1 –3 exhibit two fully reversible oxidation waves, and complexes2 and3 with electron‐rich and π‐conjuagted bridge ligands are characterized by excellent electrochemical properties. Furthermore, the larger ν(C ≡ C) separation from the IR spectroelectrochemical results of2 and3 and the intense NIR absorption features of singly oxidized species2 + and3 + revealed that their molecular skeletons have superior abilities to delocalize the positive charge. The spin density distribution from DFT calculations proved the conclusions of this study. Abstract : Dinuclear ruthenium complexes1 –3 were prepared and characterized using NMR and elemental analysis. Their redox and electronic properties were investigated by cyclic voltammetry, square‐wave voltammograms and spectroelectrochemical methods in combined with DFT calculations.