title: Unexpectedly Facile Rh(I) Catalyzed Polymerization of Ethynylbenzaldehyde Type Monomers: Synthesis of Polyacetylenes Bearing Reactive and Easy Transformable Pendant Carbaldehyde Groups.
abstract: The chain coordination polymerization of (ethynylarene)carbaldehydes with unprotected carbaldehyde groups, namely ethynylbenzaldehydes, 1-ethynylbenzene-3,5-dicarboxaldehyde, and 3-[(4-ethynylphenyl)ethynyl]benzaldehyde, is reported for the first time. Polymerization is catalyzed with various Rh(I) catalysts and yields poly(arylacetylene)s with one or two pendant carbaldehyde groups per monomeric unit. Surprisingly, the carbaldehyde groups of the monomers do not inhibit the polymerization unlike the carbaldehyde group of unsubstituted benzaldehyde that acts as a strong inhibitor of Rh(I) catalyzed polymerization of arylacetylenes. The inhibition ability of carbaldehyde groups in (ethynylarene)carbaldehydes seems to be eliminated owing to a simultaneous presence of unsaturated ethynyl groups in (ethynylarene)carbaldehydes. The reactive carbaldehyde groups make poly[(ethynylarene)carbaldehyde]s promising for functional appreciation via various postpolymerization modifications. The introduction of photoluminescence or chirality to poly(ethynylbenzaldehyde)s via quantitative modification of their carbaldehyde groups in reaction with either photoluminescent or chiral primary amines under formation of the polymers with Schiff-base-type pendant groups is given as an example.
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 43, Prague 2, Czech Republic.
authors.forename: Jan
authors.initials: J
authors.lastname: Sedláček
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 43, Prague 2, Czech Republic.
authors.forename: Lucie
authors.initials: L
authors.lastname: Havelková
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 43, Prague 2, Czech Republic.
authors.forename: Jiří
authors.initials: J
authors.lastname: Zedník
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 43, Prague 2, Czech Republic.
authors.forename: Radek
authors.initials: R
authors.lastname: Coufal
authors.affiliation: Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 43, Prague 2, Czech Republic.
authors.forename: Tomáš
authors.initials: T
authors.lastname: Faukner
authors.affiliation: J. Heyrovský Institute of Physical Chemistry, v. v. i., Academy of Sciences of the Czech Republic, Dolejsˇkova 3, 182 23, Prague 8, Czech Republic.
authors.forename: Hynek
authors.initials: H
authors.lastname: Balcar
authors.affiliation: Institute of Macromolecular Chemistry, v. v. i., Academy of Sciences of the Czech Republic, Heyrovský Sq. 2, 16206, Prague 6, Czech Republic.
authors.forename: Jiří
authors.initials: J
authors.lastname: Brus
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D001547:Benzaldehydes / Q000737:chemistry*; D002384:Catalysis; D008956:Models, Chemical; D015394:Molecular Structure; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry; D053279:Polyynes / Q000138:chemical synthesis / Q000737:chemistry*; D066244:Proton Magnetic Resonance Spectroscopy; D013050:Spectrometry, Fluorescence
chemical_list: D000447:Aldehydes; D001547:Benzaldehydes; D011108:Polymers; C413250:ethynylbenzaldehyde; D053279:Polyynes
keywords: Rh catalysts; ethynylbenzaldehydes; inhibition of polymerization; polyacetylenes; postpolymerization modification