Living ROMP Syntheses and Redox Properties of Triblock Metallocopolymer Redox Cascades

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• 作者：Haibin Gu ; Roberto Ciganda ; Patricia Castel ; Jaime Ruiz ; Didier Astruc
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：July 12, 2016
• 年：2016
• 卷：49
• 期：13
• 页码：4763-4773
• 全文大小：613K
• 年卷期：0
• ISSN：1520-5835

文摘

A number of reports have described the synthesis by ring-opening metathesis polymerization (ROMP) of diblock metallopolymers containing ferrocene and organocobalt complexes using the very efficient Grubb’s third-generation metathesis catalyst. Here the first triblock metallocopolymers are reported using this catalyst with ferrocenyl, pentamethylferrocenyl, and cobalticenyl groups in the side chains of a polynorbornene backbone. Among the six possible synthetic schemes for the successive ROMP reactions of the blocks, two of them have been successfully conducted with adequate characterization using the end-group analysis, MALDI-TOF mass spectroscopy, and Bard–Anson’s electrochemical method. The cyclic voltammetry studies showed that the integrity of reversible redox systems was preserved in cascades of heterogeneous electron transfers in both metallocopolymers with significant adsorption and electrostatic effects. This research paves the way for the design and synthesis of multiblock metallocopolymers offering access to multiproperty nanomaterials.