Anion-regulated electronic communication in a cyclometalated diruthenium complex with a urea bridge

A combined study of electrochemical measurements, intervalence charge transfer analysis, and DFT calculations suggests that the degree of urea-mediated electronic coupling between two cyclometalated ruthenium sites is enhanced by the coordination of urea with Br − or Cl − via hydrogen bonding. In co...

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Published inPhysical chemistry chemical physics : PCCP Vol. 19; no. 13; pp. 8902 - 8907
Main Authors Gong, Zhong-Liang, Deng, Li-Ye, Zhong, Yu-Wu, Yao, Jiannian
Format Journal Article
LanguageEnglish
Published England 2017
Subjects
Anions
Coupling
Coupling (molecular)
Electronics
Hydrogen bonding
Mathematical analysis
Ruthenium
Ureas
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Summary:A combined study of electrochemical measurements, intervalence charge transfer analysis, and DFT calculations suggests that the degree of urea-mediated electronic coupling between two cyclometalated ruthenium sites is enhanced by the coordination of urea with Br − or Cl − via hydrogen bonding. In contrast, the redox waves of the diruthenium complex become highly irreversible in the presence of relatively strong basic anions such as H 2 PO 4 − , F − , or OAc − . This work demonstrates that the anion–urea interaction can be employed to regulate the electronic coupling and electron transfer between redox-active sites, suggesting the potential applications of the urea-functionalized diruthenium complex in anion sensing and stimuli-responsive molecular electronics.
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ISSN:1463-9076
1463-9084
1463-9084
DOI:10.1039/C6CP08019G