Polymerization of an optically active phenylacetylene derivative bearing an azide residue by click reaction and reaction with a rhodium catalyst

Kobayashi, Shinzo; Itomi, Ken; Morino, Kazuhide; Iida, Hiroki; Yashima, Eiji

doi:10.1039/b806343e

Cited by 24 publications

(17 citation statements)

References 32 publications

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“…This hypothesis is supported by the fact that the poly-1L maintains its rigid rod-like feature in dilute benzene at 251 C because the persistent length of poly-1L estimated in dilute toluene solution, an analogous solvent to benzene, is extremely high (126 nm) at 251 C. 26 In contrast, the copolymers and homopolymer showed very intense ICDs in nonpolar CCl 4 ( Figure 3A), less polar tetrachloroethane (TCE; Figure 4A) and polar THF (Supplementary Figure S3A) even at 25 1C, and their ICD patterns in CCl 4 and benzene at 6 1C are almost mirror images to those in TCE and THF, indicating the inversion of the helicity of the polymer backbones that took place assisted by the solvent polarity, as reported previously for poly-1L, 26 poly(1L m -co-Aib n ) 19 and other dynamic helical polyacetylenes. [36][37][38][39][40][41][42][43][44] The CD and absorption spectral patterns in CCl 4 , TCE and THF were almost temperature-independent.…”

Section: Amplification Of Macromolecular Helicity In Poly(phenylacetymentioning

confidence: 99%

Amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s bearing non-racemic alanine pendants in dilute solution, liquid crystal and two-dimensional crystal

Ohsawa

Sakurai

Nagai

et al. 2011

Polym J

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Optically active poly(phenylacetylene) copolymers composed of non-racemic phenylacetylenes bearing L-and D-alanine decyl esters as the side groups (poly(1L m -co-1D n ), m4n) were prepared by the copolymerization of the corresponding L-and D-phenylacetylenes with different enantiomeric excesses using a rhodium catalyst; their chiral amplification of the helical conformation as an excess of one-handedness in a dilute solution, in a lyotropic liquid-crystalline (LC) state and in a twodimensional (2D) crystal on substrate was investigated by measuring the circular dichroism spectra of the copolymers at different temperatures, mesoscopic cholesteric twist in the LC state (cholesteric helical pitch) and high-resolution atomic force microscopy images of the self-assembled 2D helix-bundle structures of the copolymer chains, respectively.

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Section: Amplification Of Macromolecular Helicity In Poly(phenylacetymentioning

confidence: 99%

Amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s bearing non-racemic alanine pendants in dilute solution, liquid crystal and two-dimensional crystal

Ohsawa

Sakurai

Nagai

et al. 2011

Polym J

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“…Furthermore, side-chain-functionalized polyurethanes (172) poly(p-phenylene-vinylenes) (178), poly(4-ethynyl-p-xylylene-co-p-xylylene)s (72), poly(fluorenes) (181,185), poly(benzoxazine)s (184), poly(phenylacetylenes) (186), poly(thiophenes) (187)(188)(189), and poly(pyrroles) (190) have been prepared via the method (F) (see Scheme 8).…”

Section: Polyaddition/polycondensation Polyaddition and Polycondensamentioning

confidence: 99%

“Click” Chemistry in Macromolecular Synthesis

Binder

Zirbs

2009

Encyclopedia of Polymer Science and Technology

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The concept of self-healing polymers requires fast and efficient crosslinking processes, ideally based on catalytic reactions. Recently, we have developed a clickbased concept to enable self-healing properties in polymeric materials, with a focus on fast crosslinking processes. Basically, liquid reagents were encapsulated and thus can be activated by a catalytic system, inherently present within the polymer-matrix. As especially the combination of self-healing properties of nanocomposite-materials in aerospace industry deems valuable in terms of property-optimization, we focus on crosslinking processes under mild conditions, based on the copper(I)-catalyzed alkyne-azide "click" cycloaddition reaction (CuAAC). Thus we have immobilized copper(I) catalysts onto the surface of nanoparticles, on the one hand to increase the stability of the catalyst and to stimulate the self-healing processes, on the other hand to enhance the properties of the polymeric nanocomposites via the presence of the nanoparticles. For this purpose the surface of different types of nanoparticles has been chemically modified, in the subsequent step immobilizing the corresponding Cu(I) catalyst coordinatively onto their surfaces. The prepared immobilized Cu(I) were extensively characterized via TGA, XRD and TEM, furthermore demonstrating and optimizing the activity of the immobilized catalyst for all types of "click"-reactions.

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“…1,3‐Dipolar Huisgen cycloaddition of the ethynyl and azide group catalyzed by copper(I) salt takes place under mild conditions and is therefore ranked among the click reactions. This highly selective reaction is tolerant to many types of functional groups42–44 and already has been successfully used for modification of polymers45–50 including PDAs (for the introduction of chromophore51 and organometallic side groups50). Thus, it may potentially be used to introduce fluorophores into PDA chains.…”

Section: Introductionmentioning

confidence: 99%

Poly(disubstituted acetylene)s With Pendant Naphthalimide‐Based Fluorophore Groups

Sivkova

Vohlı́dal

Bláha

et al. 2012

Macro Chemistry & Physics

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New stable polyacetylenes whose quantum yield of fl uorescence is increased up to 62% because of the presence of pendant 4-(piperidine-1-yl)-1,8-naphtalimide groups are described. The polymers are prepared by two-step modifi cation of copolymers of 1-(4-tert -butylphenyl)-6-chlorohex-1-yne and 1-phenylhex-1-yne consisting of the exchange of chlorine atoms at side groups for azide groups and subsequent Huisgen click reaction of the azide groups with ethynyl groups of N -(prop-1-yne-3-yl)-4-(piperidine-1-yl)-1,8-naphthalimide. Modifi cation is evidenced by 1 H NMR, IR, Raman and UV-vis spectroscopy. Modifi ed polymers show the excitation energy transfer from their main chains on fl uorophores and nearly preservation of fl uorescence properties of fl uorophores upon their binding to polymer chains.

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Polymerization of an optically active phenylacetylene derivative bearing an azide residue by click reaction and reaction with a rhodium catalyst

Cited by 24 publications

References 32 publications

Amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s bearing non-racemic alanine pendants in dilute solution, liquid crystal and two-dimensional crystal

Amplification of macromolecular helicity of dynamic helical poly(phenylacetylene)s bearing non-racemic alanine pendants in dilute solution, liquid crystal and two-dimensional crystal

“Click” Chemistry in Macromolecular Synthesis

Poly(disubstituted acetylene)s With Pendant Naphthalimide‐Based Fluorophore Groups

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