Solid-State Polymerization of Monomers Possessing Two Diphenylbutadiyne Moieties with Amido Groups to Form Ladder Polymers

Matsuo, H; Okada, Shuji; Nakanishi, Hachiro; Matsuda, Hiro; Takaragi, Shigeru

doi:10.1295/polymj.34.825

Cited by 12 publications

(5 citation statements)

References 25 publications

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“…Nanostructures comprised of diphenyl DAs 4 and 5 placed the reactive diynes in proper position to allow for successful topochemical polymerizations (Figure S18, SI). This is remarkable because there are very few reports of successful diphenyl DA polymerizations. − The peptide assembly energetics thus override unfavorable steric or quadrupole stacking within the nanostructures while affording a dynamic environment to promote cross-linking. The nanostructures obtained after assembly of 4 were dispersed in water and irradiated with UV light (254 nm) and the formation of PDA monitored by absorption spectroscopy (Figure b).…”

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Synthesis and Alignment of Discrete Polydiacetylene-Peptide Nanostructures

et al. 2012

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Oligopeptides bearing internal diacetylene units are shown to self-assemble in water into one-dimensional nanostructures and aligned macroscopic hydrogels. The diacetylene units can be photopolymerized into polydiacetylenes that run coincident to the nanostructure and noodle long axes, and the resulting nanostructures show evidence for ambipolar charge transport. This self-assembly, alignment and polymerization technique provides a rapid way to produce globally aligned collections of conjugated polymer chains.

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Synthesis and Alignment of Discrete Polydiacetylene-Peptide Nanostructures

et al. 2012

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“…To the best of our knowledge, very few topochemical polymerizations of butadiyne through irradiation with UV light have been reported when aryl groups were attached to both ends of the butadiyne . This reaction is very difficult to achieve in crystals since the phenyl groups are expected to be too bulky to undergo significant conformational changes within the crystal.…”

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“…Unlike the case of compound 1 , the resulting solid is not soluble in methanol but readily soluble in THF. After purification of the dark material using a Soxhlet apparatus in methanol, only the polymer P1 was recovered (with trace amounts of the starting material) for a polymerization yield of 75% yield, which is quite higher than the previous yields reported for similar topochemical reactions . More importantly, size-exclusion chromatography (SEC) analysis shows a molecular weight of 27.9 kDa with a polydispersity index of only 1.8, which is surprinsingly low for a solid-state polymerization.…”

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Topochemical Polymerization of a Diarylbutadiyne Derivative in the Gel and Solid States

2011

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A diarylbutadiyne derivative was synthesized using a few steps and gelified in aromatic solvents. The gel prepared at low concentration is made of micrometers-long nanofibrils as shown by scanning electron microscopy. XRD of the dried gel shows sharp features, revealing a well-organized material. A topochemical reaction was performed on the dried gel, and a polydiacetylene presenting reversible thermochromism properties was obtained.

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“…In this connection, we have synthesized ladder-type PDAs, in which two polymer backbones were introduced in a repeating unit. 11,12 In addition, several PDAs with p-conjugated substituents, such as aromatic rings and C-C multiple bonds, directly bound to the polymer backbone [13][14][15][16][17][18][19][20][21][22] have been synthesized to obtain PDAs with absorption maxima at longer wavelengths, resulting in larger w (3) -values. In particular, oligoyne derivatives with five or more conjugated acetylenes yielded ladder polymers with p-conjugation between two PDA backbones, as shown in Figure 1.…”

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Solid-state polymerization of conjugated hexayne derivatives with different end groups

Inayama

Tatewaki

Okada

2009

Polym J

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Three hexayne derivatives with different end groups-that is, 10,12,14,16,18,20-triacontahexayne-1,30-diol (1) and its diphenylurethane (2) and diphenylester (3)-were synthesized, and their solid-state polymerization behaviors were investigated. All three monomers were thermally polymerizable. Polymers from 1 and 2 showed an absorption maximum at about 730 nm, indicating that linear polydiacetylenes (PDAs) with octatetraynyl substituents were synthesized. However, broad absorption bands in the near-infrared region were only observed for 2 at 980 and 860 nm, indicating that regular polymerization occurred in 2 to give ladder-type PDA. On the other hand, a polymer from 3 showed a visible absorption increase but no clear absorption maximum. It was estimated that intermolecular hydrogen bonding between hexayne monomers helps to form polymerizable stacks in 1 and 2. In particular, urethane groups are more effective, and 2 showed the highest reactivity in this study with an ordered interlayer structure even after a two-step solid-state polymerization to give ladder-type PDA. Keywords: ladder polymer; polydiacetylene; solid-state polymerization; p-conjugated polymer Some butadiyne compounds are polymerized in the solid state by ultraviolet irradiation or by thermal treatment. This solid-state polymerization was clarified by Wegner 1 as a single-crystal-to-singlecrystal topochemical transition to yield polydiacetylene (PDA), which is classified as a one-dimensional p-conjugated polymer. Since the reaction is topochemically controlled, the reactivity of butadiyne monomers is greatly affected by their packing in crystals. 2 In fact, when the butadiyne monomers in crystals have a stacking distance d of about 5 Å between adjacent molecules in the array and an angle y of about 45 1 between the butadiyne rod and stacking axis, 1,4-addition polymerization occurs. Since molecular packing in crystals is determined by the intermolecular interactions between monomers, the selection of substituents attached to the butadiyne moiety is quite important in the preparation of PDAs. On the other hand, much research on the physical properties of PDAs, such as electrical, 3,4 chromic 5-7 and nonlinear optical (NLO) [8][9][10] properties, which originate from the p-conjugated backbone structure, have been undertaken. In particular, the third-order NLO properties of PDAs have attracted interest. To achieve larger NLO susceptibility (w (3) ) in PDA, it is necessary to increase the density of the p-conjugated polymer backbone and the p-electron number in a repeating unit. In this connection, we have synthesized ladder-type PDAs, in which two polymer backbones were introduced in a repeating unit. 11,12 In addition, several PDAs with p-conjugated substituents, such as aromatic rings and C-C multiple bonds, directly bound to the polymer backbone [13][14][15][16][17][18][19][20][21][22] have been synthesized to obtain PDAs with absorption maxima at longer wavelengths, resulting in larger w (3) -values. In particular, oligoyne derivatives with five...

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Solid-State Polymerization of Monomers Possessing Two Diphenylbutadiyne Moieties with Amido Groups to Form Ladder Polymers

Cited by 12 publications

References 25 publications

Synthesis and Alignment of Discrete Polydiacetylene-Peptide Nanostructures

Synthesis and Alignment of Discrete Polydiacetylene-Peptide Nanostructures

Topochemical Polymerization of a Diarylbutadiyne Derivative in the Gel and Solid States

Solid-state polymerization of conjugated hexayne derivatives with different end groups

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