“…The high conversion of ethynyl groups achieved in the homopolycyclotrimerization of I , II, and III allowed to discuss the architecture of P( I ), P( II ), and P( III ). Two distinct propagation modes, (i) branching and (ii) crosslinking, may participate in the homopolycyclotrimerization of diethynylated monomers, regardless of the type (internal/terminal) of their ethynyl groups . The benzene–triyl links created through the branching propagation mode are formed via reaction of three ethynyl groups from three different polymer, oligomer, or monomer molecules.…”
This study reports the first Co (CO) -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 g ), which is particularly important in the case of soluble polyphenylenes because they can be potentially used to prepare microporous layers.
“…The high conversion of ethynyl groups achieved in the homopolycyclotrimerization of I , II, and III allowed to discuss the architecture of P( I ), P( II ), and P( III ). Two distinct propagation modes, (i) branching and (ii) crosslinking, may participate in the homopolycyclotrimerization of diethynylated monomers, regardless of the type (internal/terminal) of their ethynyl groups . The benzene–triyl links created through the branching propagation mode are formed via reaction of three ethynyl groups from three different polymer, oligomer, or monomer molecules.…”
This study reports the first Co (CO) -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 g ), which is particularly important in the case of soluble polyphenylenes because they can be potentially used to prepare microporous layers.
“…The ethynyl groups of the monomer molecules are transformed into polyene (polyacetylene)‐type conjugated main chains in this polymerization (see Scheme depicting the polymerization of phenylacetylene to linear poly(phenylacetylene)). Recently, we found that Rh I catalysts also polymerized diethynylarenes (diethynylbenzenes and 4,4'‐diethynylbiphenyl), and mixtures of diethynylarenes with monoethynylarenes . In this case, the polymerization provided nonswellable polyacetylene networks with permanent microporosity in which the polyene chains were cross‐linked with arylene links.…”
Section: Resultsmentioning
confidence: 99%
“…We have recently published the preparation of highly rigid hyper‐cross‐linked porous polymers by chain‐growth (coordination) polymerization of diethynylarenes (specifically diethynylbenzenes) or by copolymerization of these monomers with monoethynylarenes . This polymerization provides micro/mesoporous polymer networks ( S BET up to 1400 m 2 g −1 ) with rigid conjugated main chains of the polyacetylene type in which double and single bonds alternate between carbon atoms.…”
Heterogeneous catalysts based on materials with permanent porosity are of great interest owing to their high specific surface area, easy separation, recovery, and recycling ability. Additionally, porous polymer catalysts (PPCs) allow us to tune catalytic activity by introducing various functional centres. This study reports the preparation of PPCs with a permanent micro/mesoporous texture and a specific surface area S of up to 1000 m g active in acid-catalyzed reactions, namely aldehyde and ketone acetalization and carboxylic acid esterification. These PPC-type conjugated hyper-cross-linked polyarylacetylene networks were prepared by chain-growth homopolymerization of 1,4-diethynylbenzene, 1,3,5-triethynylbenzene and tetrakis(4-ethynylphenyl)methane. However, only some ethynyl groups of the monomers (from 58 to 80 %) were polymerized into the polyacetylene network segments while the other ethynyl groups remained unreacted. Depending on the number of ethynyl groups per monomer molecule and the covalent structure of the monomer, PPCs were decorated with unreacted ethynyl groups from 3.2 to 6.7 mmol g . The hydrogen atoms of the unreacted ethynyl groups served as acid catalytic centres of the aforementioned organic reactions. To the best of our knowledge, this is first study describing the high activity of hydrogen atoms of ethynyl groups in acid-catalyzed reactions.
“…The internal alkyne-based polycyclotrimerization reactions, however, have been rarely reported. 25,26 This may be due to the low reactivity of sterically hindered internal alkynes. It is well-known that new polymerization methodologies are mainly derived from highly efficient organic reactions.…”
Alkyne polycyclotrimerizations have become efficient synthetic tools for constructing hyperbranched polyphenylenes. However, the polycyclotrimerization reactions of internal alkynes are rarely reported. Herein, we present the first example of RhCl 3 -catalyzed polycyclotrimerization of activated internal diynes to prepare hyperbranched polymers. The polymerization reactions of diphenylpropiolates (1a−c) were performed in toluene under reflux in the presence of RhCl 3 •3H 2 O and N,N-diisopropylethylamine (DIPEA), affording soluble hyperbranched poly-(triphenylbenzoate)s (hb-PTPBs), hb-P1a−c, with high molecular weights (up to 187000) and high regioregularities (fraction of 1,2,4-triphenylbenzoate isomer up to 88.2%) in satisfactory yields. The degree of branching of hb-P1a was determined to be 0.73. The resultant hb-PTPBs are thermally stable, with 5% weight loss temperatures higher than 330 °C. The hb-PTPBs are weakly emissive in their dilute solutions but become intensively emissive upon aggregate formation, showing aggregation-induced emission features.
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