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Novel materials from bis(arene)metal‐containing polyacrylonitrile
Author(s) -
Domrachev George A.,
Klapshina Larisa G.,
Semenov Vladimir V.,
Douglas William E.,
Antipov Oleg L.,
Kuzhelev Alexander S.,
Sorokin Alexey A.
Publication year - 2001
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/1099-0739(200101)15:1<51::aid-aoc116>3.0.co;2-9
Subject(s) - chemistry , polyacrylonitrile , acrylonitrile , mesitylene , polymer chemistry , acetonitrile , chromium , molecule , metal , electron paramagnetic resonance , solvent , polymer , photochemistry , organic chemistry , toluene , physics , nuclear magnetic resonance , copolymer
Novel bis(arene)metal‐containing polyacrylonitrile materials have been prepared by the polycyanoethylation reaction between acrylonitrile and (arene) 2 M (M = Cr or V; arene = PhH, C 6 H 4 Et 2 or mesitylene) in the absence of solvent. The resulting star‐shaped molecules consist of a central (arene) 2 M species with up to four polyacrylonitrile arms covalently bonded to the arene ligands. The materials are readily soluble and films can be cast from solutions in acetonitrile. The IR and solid state 13 C NMR spectra (or EPR spectrum for the oxidized chromium‐containing polymer) are consistent with the presence of a metal–arene bond and confirm the persistence of the sandwich structure. The properties of the thermolysed materials are consistent with the formation of conjugated naphthyridine‐type structures. The value of | n 2 | determined by the degenerate four‐wave mixing technique at 1064 nm with a 6 ns pulse duration for a solution in conc. H 2 SO 4 (1 g l −1 ) of the chromium‐containing polymer pyrolysed at 350 °C was found to be 0.8 × 10 −13 cm 2 W −1 corresponding to |lRe χ (3) | = 0.4 × 10 −11 esu.