Premium
Photocontrolled Living Anionic Polymerization of Phosphorus‐Bridged [1]Ferrocenophanes: A Route to Well‐Defined Polyferrocenylphosphine (PFP) Homopolymers and Block Copolymers
Author(s) -
Patra Sanjib K.,
Whittell George R.,
Nagiah Simone,
Ho CheukLam,
Wong WaiYeung,
Manners Ian
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902886
Subject(s) - copolymer , monomer , chemistry , trimethylsilyl , polymerization , living anionic polymerization , polymer chemistry , ring opening polymerization , anionic addition polymerization , silane , phosphorus , polymer , medicinal chemistry , organic chemistry
Phosphorus‐bridged strained [1]ferrocenophanes [Fe{(η‐C 5 H 4 ) 2 P(CH 2 CMe 3 )}] ( 2 ) and [Fe{(η‐C 5 H 4 ) 2 P(CH 2 SiMe 3 )}] ( 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‐C 5 H 4 ) 2 P(CMe 3 )}] ( 1 ) and the new monomers 2 and 3 , initiated by Na[C 5 H 5 ] in THF at 5 °C, yielded well‐defined polyferrocenylphosphines (PFPs), [Fe{(η‐C 5 H 4 ) 2 PR}] n (R=CMe 3 ( 4 ), CH 2 CMe 3 ( 5 ), and CH 2 SiMe 3 ( 6 )), with controlled molecular weights (up to ca. 60×10 3 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‐PFS F ( 7 a and 7 b ) (PFS F =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 PFS F domains in a PFP matrix.