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Photocontrolled Living Anionic Polymerization of Phosphorus-Bridged [1]Ferrocenophanes: A Route to Well-Defined Polyferrocenylphosphine (PFP) Homopolymers and Block Copolymers

  1. Sanjib K. Patra Dr.1,
  2. George R. Whittell Dr.1,
  3. Simone Nagiah1,
  4. Cheuk-Lam Ho1,2,
  5. Wai-Yeung Wong Prof.2,
  6. Ian Manners Prof.1

Article first published online: 16 FEB 2010

DOI: 10.1002/chem.200902886

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 16, Issue 10, pages 3240–3250, March 8, 2010

Additional Information

How to Cite

Patra, Sanjib K., Whittell, George R., Nagiah, S., Ho, C.-L., Wong, W.-Y. and Manners, I. (2010), Photocontrolled Living Anionic Polymerization of Phosphorus-Bridged [1]Ferrocenophanes: A Route to Well-Defined Polyferrocenylphosphine (PFP) Homopolymers and Block Copolymers. Chem. Eur. J., 16: 3240–3250. doi: 10.1002/chem.200902886

Author Information

  1. 1

    School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS (UK), Fax: (+44) 117-929-0509

  2. 2

    Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong (P. R. China), Fax: (+852) 3411-7348

Publication History

  1. Issue published online: 1 MAR 2010
  2. Article first published online: 16 FEB 2010
  3. Manuscript Received: 19 OCT 2009

Funded by

  • EPSRC
  • European Union
  • Hong Kong Research Grants Council. Grant Number: HKBU202508
  • Hong Kong Baptist University. Grant Number: FRG/07-08/II-65

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Keywords:

  • block copolymers;
  • metallopolymers;
  • phosphanes;
  • photolysis;
  • self-assembly

Abstract

Phosphorus-bridged strained [1]ferrocenophanes [Fe{(η-C5H4)2P(CH2CMe3)}] (2) and [Fe{(η-C5H4)2P(CH2SiMe3)}] (3) with neopentyl and (trimethylsilyl)methyl substituents on phosphorus, respectively, have been synthesized and characterized. Photocontrolled living anionic ring-opening polymerization (ROP) of the known phosphorus-bridged [1]ferrocenophane [Fe{(η-C5H4)2P(CMe3)}] (1) and the new monomers 2 and 3, initiated by Na[C5H5] in THF at 5 °C, yielded well-defined polyferrocenylphosphines (PFPs), [Fe{(η-C5H4)2PR}]n (R=CMe3 (4), CH2CMe3 (5), and CH2SiMe3 (6)), with controlled molecular weights (up to ca. 60×103 Da) and narrow molecular weight distributions. The PFPs 4–6 were characterized by multinuclear NMR spectroscopy, DSC, and by GPC analysis of the corresponding poly(ferrocenylphosphine sulfides) obtained by sulfurization of the phosphorus(III) centers. The living nature of the photocontrolled anionic ROP allowed the synthesis of well-defined all-organometallic PFP-b-PFSF (7 a and 7 b) (PFSF=polyferrocenylmethyl(3,3,3,-trifluoropropyl)silane) diblock copolymers through sequential monomer addition. TEM studies of the thin films of the diblock copolymer 7 b showed microphase separation to form cylindrical PFSF domains in a PFP matrix.

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