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Home  >  Journal list  >  Polymer Journal  >  Vol.45  No.2 (2013)  >  pp.216-225

Polymer Journal
<<Previous article Vol.45  No.2 (2013)   pp.216 - 225 Next article>>

Synthesis of miktoarm star copolymer Ru(II) complexes by click-to-chelate approach

Nao Xiao1, Yougen Chen1, Xiande Shen2, Chunhong Zhang2, Shigenobu Yano3, Michael Gottschaldt4, Ulrich S Schubert4, Toyoji Kakuchi1 and Toshifumi Satoh1
1Division of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, Japan
2College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin, China
3Graduate School of Materials Science, Nara Institute of Science and Technology, Nara, Japan
4Laboratory for Organic and Macromolecular Chemistry, Friedrich-Schiller-University Jena, Jena, Germany

A series of AB2-, ABC-, (AB)2-, A2B2- and ABCD-type miktoarm copolymer Ru(II) complexes was synthesized by a stepwise chelating method, which involved the first-step chelating reaction of Ru(II)(DMSO)4Cl2 with a polymer-substituted 2-(1H-1,2,3-triazol-4-yl)pyridine (tapy) or 2,6-bis(1H-1,2,3-triazol-4-yl)pyridine (bitapy) ligand to produce a stable polymer Ru(II) mono-complex, and a second-step chelating reaction of the polymer Ru(II) mono-complex with another tapy or bitapy ligand to afford the miktoarm copolymer Ru(II) complexes. In order to synthesize them, the polymer-substituted tapy and bitapy ligands were first prepared by the click reaction of azido-terminated polymers with 2-ethynylpyridine and 2,6-diethynylpyridine, respectively. The azido-terminated polystyrene (PS) and poly(n-butyl acrylate) (PBA) were prepared by the atom-transfer radical polymerizations of styrene and n-butyl acrylate using ethyl 2-bromoisobutyrate as the initiator, followed by the substitutions of their end bromines with an azido group, respectively. The azido-terminated poly(n-hexyl isocyanate) was prepared by the living coordination polymerization of n-hexyl isocyanate using dichloro(cyclopentadienyl)(6-azidohexyloxy)titanium that was prepared by mixing 6-azido-1-hexanol with trichloro(cyclopentadienyl)titanium before the polymerization. The azido-terminated poly(styrene oxide) and poly(ε-caprolactone) were synthesized by the controlled/living ring-opening polymerizations of ε-caprolactone using diphenyl phosphate as the catalyst and of styrene oxide using the phosphazene base of t-Bu-P4 as the catalyst, respectively, in which 6-azido-1-hexanol was used as the initiator.


Keyword:
click chemistry; miktoarm star copolymer; Ru(II) complexes; stepwise chelating

Received: April 06, 2012
Accepted: April 27, 2012 , Published online: June 13, 2012
© 2013 The Society of Polymer Science, Japan

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