Citation: ZHANG Xiao-Yong, HAN Li-Min, GAO Yuan-Yuan, JIA Hui-Jie, SUO Quan-Ling. Designed Syntheses and Electrochemistry Properties of Alkynyl-Bridged Asymmetric Phenyl Substituted Biferrocenyl Derivatives[J]. Chinese Journal of Inorganic Chemistry, ;2018, 34(5): 864-873. doi: 10.11862/CJIC.2018.109 shu

Designed Syntheses and Electrochemistry Properties of Alkynyl-Bridged Asymmetric Phenyl Substituted Biferrocenyl Derivatives

1.
Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051, China
2.
Department of Chemistry, Baotou Teachers' College, Baotou, Inner Mongolia 014030, China

Corresponding author: SUO Quan-Ling, szj010062@163.com
Received Date: 20 November 2017
Revised Date: 9 March 2018

Figures(8)

Three asymmetric alkynyl-bridged pentaphenyl substituted biferrocenyl derivatives Fc'-C≡C-Fc (1), Fc'-C≡C-C≡C-Fc (2) and Fc'-C≡C-C≡C-Fc' (3) (Fc'=pentaphenylferrocenyl, Fc=ferrocenyl) were successfully synthesized by eight successive reaction steps using tetraphenylcyclopentadienone as starting material. In the process gaining compounds 1~3, three intermediate products Fc'-COCH₃ (5), Fc'-CCl=CHCHO (6) and Fc'-C≡CH (7) were also obtained by three-step continuous reaction using known compound Fc'H (4) prepared by four-step reaction. The crystal structures of compounds 1, 2 and 5, 7 were determined by X-ray single crystal diffraction technique, and the electrochemical properties of compounds 1~7 were studied by cyclic voltammetry. The results show the C-H…π interactions and the steric hindrance result in the different space orientations of Fc' and Fc units in the crystals of 1 and 2. The redox potential of the iron center is increased (E_p^a(Fc'-H)=0.658 V, E_p^a (Fc-H)=0.511 V) while five phenyls are introduced into a five-membered ring of ferrocenyl unit. Comparing with known compounds Fc-C≡C-Fc and Fc-C≡C-C≡C-Fc (ΔE_Fc-C≡C-Fc=0.215 V, ΔE_{Fc-C≡C-C≡C-Fc}=0.134 V), the oxidation potential differences (ΔE) of 1~3 are all elevated (ΔE₁=0.236 V; ΔE₂=0.170 V; ΔE₃=0.146 V). In comparison with 1 and Fc-C≡C-Fc, with 2 and Fc-C≡C-C≡C-Fc and 3, we discover the ΔE values of corresponding compounds were significantly enhanced while two different groups Fc' and Fc are bridged into alkynyl linkage.
- pentaphenylferrocenylacetylene,
- alkynyl-bridged phenyl substituted biferrocenyl,
- designed synthesis,
- electrochemical property,
- crystal structure
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沈阳化工大学材料科学与工程学院沈阳 110142