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Polyferrocenylsilane homopolymers and diblock copolymers with pendant ruthenocenyl groups by photocontrolled ring-opening polymerisation

Polyferrocenylsilane homopolymers and diblock copolymers with pendant ruthenocenyl groups by photocontrolled ring-opening polymerisation

Erhard, Maximilian, Lam, Kevin ORCID: 0000-0003-1481-9212, Haddow, Mairi, Whittell, George R, Geiger, William E and Manners, Ian (2013) Polyferrocenylsilane homopolymers and diblock copolymers with pendant ruthenocenyl groups by photocontrolled ring-opening polymerisation. Polymer Chemistry, 5 (4). pp. 1264-1274. ISSN 1759-9954 (Print), 1759-9962 (Online) (doi:https://doi.org/10.1039/c3py01232h)

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Abstract

The strained, sila[1]ferrocenophane [{Fe(η-C5H4)2}SiMe(η-C5H4)Ru(η-C5H5)] (4) has been prepared by the reaction of Li[(η-C5H4)Ru(η-C5H5)] (8) with [{Fe(η-C5H4)2}SiMeCl] (7). Two different routes for the synthesis of 8 were investigated, which differed predominately in the purity of the product obtained. Although the thermal ring-opening polymerisation (ROP) of 4 failed to yield soluble polymeric material, photocontrolled ROP using Na[C5H5] as the initiator afforded relatively monodisperse, soluble polymers of predetermined molecular weights and the general formula [(η-C5H4)Fe(η-C5H4)SiMe{(η-C5H4)Ru(η-C5H5)}]n (19). This material was stable to both oxygen and moisture. Electrochemical characterisation of 4 revealed unusual, concentration dependent behaviour as a consequence of the oxidation of the ruthenocenyl groups. This phenomenon was not observed upon oxidation of the Ru centres in 19, presumably due to the sterically encumbered structure of the polymer. The photocontrolled ROP protocol was extended to afford the block copolymers polystyrene (PS)n-b-[(η-C5H4)Fe(η-C5H4)SiMe{(η-C5H4)Ru(η-C5H5)}]m (22) by the application of a PS-based macroinitiator. These materials represent rare examples of complex polymer architectures where two different metals are incorporated in the same block.

Item Type: Article
Uncontrolled Keywords: Electrochemistry, Organometallics, Polymers
Subjects: Q Science > QC Physics
Q Science > QD Chemistry
Faculty / Department / Research Group: Faculty of Engineering & Science
Faculty of Engineering & Science > Department of Pharmaceutical, Chemical & Environmental Sciences
Last Modified: 09 Oct 2017 15:04
Selected for GREAT 2016: None
Selected for GREAT 2017: None
Selected for GREAT 2018: None
Selected for GREAT 2019: None
URI: http://gala.gre.ac.uk/id/eprint/17725

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