Solid-State Polymerization of Monophenylbutadiyne Derivatives

Watanabe, Junichi; Yokoyama, Harumi; Okada, Shuji; Takaragi, Shigeru; Matsuda, Hiro; Nakanishi, Hachiro

doi:10.1080/15421400902950030

Cited by 6 publications

(3 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6b, although the 4b cast film was confirmed to be amorphous by the broad diffraction peaks at 2θ = 22°, several peaks implied partial regular structures. 28 After UV irradiation and washing with acetone, the crystallinity of the 4b cast film was almost lost and completely amorphous, respectively. Similar sharp peaks at 2θ = 24°(3.67 Å), attributed to the π-π distance between the molecules, have been observed in different solidified forms (Fig.…”

Section: Xrd Analysismentioning

confidence: 99%

See 1 more Smart Citation

Topochemical polymerization of unsymmetrical aryldiacetylene supramolecules with nitrophenyl substituents utilizing C–H⋯π interactions

Wang

Liu

et al. 2015

Org. Biomol. Chem.

Self Cite

View full text Add to dashboard Cite

Diacetylenes are versatile building blocks, in which many functional groups can be incorporated for the construction of new materials with desirable properties. In this study, 6-(p or m-nitrophenyl)-3,5-hexadiyne-1-ol (4a or 4b) containing nitrophenyl groups (host) and 2-hydroxyethyl groups (guest) in different diacetylene terminals were designed to establish an ordered supramolecular assembly that is complied with the strict requirements for the topochemical polymerization of diacetylenes. Crystal film and bulk crystals of compound 4b were obtained successfully by cast film and re-precipitation methods. Both of these could photopolymerize to the corresponding regular poly(diacetylene) polymer, as evidenced by UV-vis, IR, FL and Raman spectroscopy. The electrochemical properties and behaviors of 4a and 4b were also investigated, and the results show that the differences between the para and meta positions of the mono-phenylacetylene substituents probably result from the topochemical polymerization. Thus, m-nitrophenylbutadiyne derivatives with sizeable C-H∙∙∙π interactions seemed to be effective for the formation of a polymerizable packing, which is appropriate for topochemical polymerization.

show abstract

Section: Xrd Analysismentioning

confidence: 99%

“…Therefore, several monophenylbutadiyne derivatives with simpler structures have been investigated. 28 However, no topochemical polymerization has been confirmed.…”

Section: Introductionmentioning

confidence: 99%

Topochemical polymerization of unsymmetrical aryldiacetylene supramolecules with nitrophenyl substituents utilizing C–H⋯π interactions

Wang

Liu

et al. 2015

Org. Biomol. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Topochemical solid-state polymerization yields single crystals with definite folded structures of polymeric chains. So far, there have been a limited number of monomers reported such as aromatic di(tri)olefins, − oligo(aza)anthracenes, − 1,3-dienes, − 1,3,5-trienes, , 1,3-diynes, − 1,3,5-triynes, − bis(indanone)s, , and carbohydrate-based and peptide-based monomers with azide and alkynes − or alkenes . Recently, syntheses of two-dimensional (2D) polymers, planar macromolecules, by topochemical cycloaddition reactions have been exploited as a new class of polymers, including applications. , The resultant linear polymers unambiguously exhibit trans-conformational folded structures according to single-crystal X-ray crystallography, but the folded structures in solution remain unsolved because of their insolubilities.…”

Section: Introductionmentioning

confidence: 99%

Preservation of the Conformational Structures of Single-Polymer Crystals in Solution

et al. 2022

View full text Add to dashboard Cite

We have found that the cis-conformational structures in single-polymer crystals obtained by solid-state polymerization are retained in solution. A soluble alternating copolymer was accidentally obtained during our research employing a series of 7,7,8,8-tetrakis(alkoxycarbonyl)-p-quinodimethanes (1) with alkoxy groups such as methoxy(1a(Me)), ethoxy(1b(Et)), propoxy(1c(Pr)), isopropoxy(1d(iPr)), butoxy(1e(Bu)), isobutoxy(1f(iBu)), pentyloxy(1g(Pen)), hexyloxy(1h(Hex)), and dodecyloxy(1i(Dod)). Thus, 1a(Me), 1b(Et), 1c(Pr), 1e(Bu), and 1g(Pen) with linear alkoxy groups afforded 1:1 charge-transfer complex crystals with 7,7,8,8-tetracyanoquinodimethane (3), while 1d(iPr), 1f(iBu), 1h(Hex), and 1i(Dod) with branching or linear long-chain alkoxy groups did not. The former crystals topochemically underwent photochemical and thermal copolymerizations via a radical mechanism to yield cis-conformational alternating copolymer crystals according to X-ray crystallography. Attractively, the rates of thermal copolymerization were found to increase roughly with an increase in the chain length of the linear alkoxy groups and/or a decrease in the reacting exomethylene carbon distances between 1 and 3. This finding led us to carry out a spontaneous copolymerization of 1g(Pen) with 3 in solution, resulting in the first synthesis of a soluble alternating copolymer during our research. Spectral analyses of the soluble copolymer of 1g(Pen) with 3, together with geometry optimization and spectroscopic simulations, proved that the cis-conformational structure was retained in solution as well as in the solid state. This provides the first spectral observation of a cis-conformational structure in solution with respect to the alternating copolymers of the p-quinodimethane derivatives.

show abstract

Solid-State Polymerization of Conjugated Acetylene Compounds to Form $$\uppi$$-Conjugated Polymers

Okada

Tatewaki

Yamakado

2020

Advances in Organic Crystal Chemistry

View full text Add to dashboard Cite

Solid-State Polymerization of Monophenylbutadiyne Derivatives

Cited by 6 publications

References 6 publications

Topochemical polymerization of unsymmetrical aryldiacetylene supramolecules with nitrophenyl substituents utilizing C–H⋯π interactions

Topochemical polymerization of unsymmetrical aryldiacetylene supramolecules with nitrophenyl substituents utilizing C–H⋯π interactions

Preservation of the Conformational Structures of Single-Polymer Crystals in Solution

Solid-State Polymerization of Conjugated Acetylene Compounds to Form $$\uppi$$-Conjugated Polymers

Contact Info

Product

Resources

About