2017
DOI: 10.1002/pola.28609
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Abstract: A cholesteryloxyallene (1) bearing chiral cholesteryl pendant group was designed and synthesized. Living polymerization of this monomer with an allylnickel complex as a catalyst give poly(cholesteryloxyallene)s (poly‐1ms) in high yields with controllable molecular weights and narrow molecular weight distributions. These polymers were found to possess a dynamic helical conformation with a preferred handedness in n‐hexane as confirmed by circular dichroism and absorption spectra as well as optical ratios. The he… Show more

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Cited by 4 publications
(5 citation statements)
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“…Allene and its derivatives are polymerizable via the 1,2- or/and 2,3-part of the cumulated double bonds by Ni­(II) catalysts, providing PAs carrying functionalizable exomethylene on the backbone. , The Ni­(II)-terminated P3HT could initiate a block copolymerization of allene monomers. For example, adding hexadecyloxyallene ( 4a ) to the solution of Ni­(II)-terminated P3HT provided P3H- b -poly­(hexadecyloxylallene)­s (poly­( 1a m - b - 4a n )­s) in good yield with a controllable M n and a low M w / M n , due to the living nature of the one-pot block copolymerization (Figure a) . The copolymerization specifically occurred on a less steric 2,3-part of the cumulated double bonds, due to the large steric dppp ligand on the Ni­(II)-catalyst.…”
Section: Ni­(ii)-catalyzed One-pot Block Copolymerizationmentioning
confidence: 99%
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“…Allene and its derivatives are polymerizable via the 1,2- or/and 2,3-part of the cumulated double bonds by Ni­(II) catalysts, providing PAs carrying functionalizable exomethylene on the backbone. , The Ni­(II)-terminated P3HT could initiate a block copolymerization of allene monomers. For example, adding hexadecyloxyallene ( 4a ) to the solution of Ni­(II)-terminated P3HT provided P3H- b -poly­(hexadecyloxylallene)­s (poly­( 1a m - b - 4a n )­s) in good yield with a controllable M n and a low M w / M n , due to the living nature of the one-pot block copolymerization (Figure a) . The copolymerization specifically occurred on a less steric 2,3-part of the cumulated double bonds, due to the large steric dppp ligand on the Ni­(II)-catalyst.…”
Section: Ni­(ii)-catalyzed One-pot Block Copolymerizationmentioning
confidence: 99%
“…Among the reported π-conjugated polymers, polythiophenes (PTs), , poly­(phenyleneethynylene)­s (PPEs), , and polyfluorenes (PFs) are widely investigated due to their high conductivity and adjustable optoelectronic characteristics. These polymers with controllable molar mass ( M n ) and narrow molecular weight distribution ( M w / M n ) are commonly prepared through the “living catalyst transfer polycondensation (CTP)”, which involve Kumada, Sonogashira, and Suzuki cross-coupling reactions using Ni­(II) or Pd­(II) catalysts. , Recently, we have developed a series of Pd­(II) and Ni­(II) catalysts, which can initiate the living polymerization of phenyl isocyanides (PIs), allenes, and dizaoacetates, and enable the controlled synthesis of helical poly­(phenyl isocyanide) (PPI), polyallene (PA), ,, and polycarbene (PC), respectively. , Combining these polymerizations with CTP, block copolymers such as PT- b -PPI, PT- b -PA, PT- b -PC, PPE- b -PPI, , PF- b -PPI, , and PF- b -PC have been prepared via the one-pot living block copolymerization of two distinct monomers (Figure c). The living block copolymerization mechanisms provided the block copolymers in high yields, controllable M n , low M w / M n , and tunable compositions.…”
Section: Introductionmentioning
confidence: 99%
“…It is universal from macroscope to microscope such as helix in the galaxy and right‐handed α‐helix in protein. Inspired by nature, a variety of helical polymers have been designed and synthesized, such as polyacetylenes, [23–25] polyisocyanides, [26–28] polyallenes, [10–12] and so forth. Among them, helical polyallenes have attracted considerable attention for the potential applications in chiral recognition and resolution, asymmetric catalysis, circularly polarized luminescence, etc.…”
Section: Preparation Of Polyallenesmentioning
confidence: 99%
“…Yu et al. prepared helical polyallenes by the living polymerization of allene monomers with chiral cholesteryl pendants catalyzed by allylnickel complex [11] . The afforded polyallenes presented a one‐handed helical conformation, which was stabilized via increase of the repeating unit until the degree of the polymerization arrived to 100.…”
Section: Preparation Of Polyallenesmentioning
confidence: 99%
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