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Homo‐ and Copolycyclotrimerization of Aromatic Internal Diynes Catalyzed with Co 2 (CO) 8 : A Facile Route to Microporous Photoluminescent Polyphenylenes with Hyperbranched or Crosslinked Architecture
Author(s) -
Sedláček Jan,
Sokol Jiří,
Zedník Jiří,
Faukner Tomáš,
Kubů Martin,
Brus Jiří,
Trhlíková Olga
Publication year - 2018
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201700518
Subject(s) - monomer , microporous material , materials science , benzene , phenylacetylene , diphenylacetylene , polymer chemistry , photoluminescence , molecule , polymer , catalysis , chemistry , organic chemistry , composite material , optoelectronics
This study reports the first Co 2 (CO) 8 ‐catalyzed [2+2+2] polycyclotrimerization by the transformation of internal ethynyl groups of aromatic diyne monomers. The reaction yields polycyclotrimers of polyphenylene‐type with either hyperbranched or partly crosslinked architecture. The homopolycyclotrimerization of the monomers with two ethynyl groups per one molecule, namely 1,4‐bis(phenylethynyl)benzene, 4,4′‐bis(phenylethynyl)biphenyl, and 4‐(phenylethynyl)phenylacetylene, gives partly crosslinked, insoluble polyphenylenes. The soluble, hyperbranched polyphenylenes are generated via copolycyclotrimerization of 1,4‐bis(phenylethynyl)benzene with 1,2‐diphenylacetylene (average number of ethynyl groups per monomer molecule < 2). This one‐step polycyclotrimerization path to hyperbranched or partly crosslinked polyphenylenes is an alternative to the synthesis of these polymers by Diels–Alder transformation of substituted cyclopentadienones. All polyphenylenes prepared exhibit photoluminescence with emission maxima ranging from 381 to 495 nm. Polyphenylenes with a less compact packing of segments are microporous (specific surface area up to 159 m 2 g −1 ), which is particularly important in the case of soluble polyphenylenes because they can be potentially used to prepare microporous layers.