The Topochemical 1,6-Polymerization of a Triene

Hoang, Tram H.; Lauher, Joseph W.; Fowler, Frank W.

doi:10.1021/ja027444a

Cited by 103 publications

(46 citation statements)

References 10 publications

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“…Recently, some examples for new kinds of topochemical and solid-state polymerizations have been reported. [153][154][155][156][157][158][159][160] Polymer syntheses in the solid state will become more important in the future.…”

Section: Resultsmentioning

confidence: 99%

Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

111

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ABSTRACT:In this review article, polymer structure control and organic material design based on polymer crystal engineering are described. The structures and properties of crystalline materials are designed using pre-organized molecules through various intermolecular interactions such as hydrogen bonds, π · · · π, CH/π, CH/O, and halogen interactions. Here, we describe the features and mechanisms of the topochemical polymerization of 1,3-diene monomers including some ester, ammonium, and amide derivatives of muconic and sorbic acids, which are 1,3-diene di-and monocarboxylic acid derivatives, respectively. We have proposed the topochemical polymerization principles for diene monomers on the basis of the crystallographic data accumulated for various kinds of diene monomers. The combination of several intermolecular interactions is useful for the construction of molecular packing appropriate for 5 Å stacking in order to facilitate the topochemical polymerization in the crystalline state. We refer to the control of polymer chain structure including tacticity, molecular weight, and ladder structure, and also polymer crystal structures, as well as the organic intercalation system using layered polymer crystals obtained by the topochemical polymerization. A totally solvent-free system for the synthesis of layered polymer crystals is also described.KEY WORDS Topochemical Polymerization / Solid-State Reaction / Crystal Engineering / Supramolecular Synthon / Stereoregular Polymer / Controlled Radical Polymerization / X-Ray Single Crystal Structure Analysis / Intercalation / Controlled polymer synthesis, including the control of polymer chain structures such as molecular weight, molecular weight distribution, chain-end structure, branching, regioselectivity, and stereoselectivity, has great potential for the design of macromolecular architecture leading to advanced nano-materials and devices. [1][2][3][4][5][6][7][8][9][10][11] All the features and functions of polymers importantly depend on primary chain structures and the manner of polymer chain assembly in crystalline and non-crystalline solids, or in a condensed state. Therefore, the control of polymer chain structures in polymer synthesis can hardly be overestimated for the architecture of advanced polymeric materials.Especially, the stereochemistry of polymers has received significant attention in both fundamental and applied fields ever since the first discoveries of stereoregular polymers in the 1950s. 12-14 Highly controlled stereospecific polymerization has been well established by coordination polymerization of olefins and diene monomers and by anionic polymerization of certain types of polar monomers. Radical polymerization is the most important and convenient process for the production of various kinds of vinyl and diene polymers due to recent achievements in well-controlled polymerizations in addition to the classical advantages of the radical process. [15][16][17][18][19][20][21][22] There are two fundamentally different ways to control of the chain structu...

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Section: Resultsmentioning

confidence: 99%

Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

111

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“…On the other hand, several examples are known in which the repeating arrangements of the monomers harmonize with the resulting polymer unit to keep single crystals even after the polymerization. The classical examples are the topochemical polymerization of distyrylpyrazines17–19 and diacetylenes,20 and some current examples are dienes,21–23 trienes,24 and quinodimethanes 25, 26. It is thought that the combined design of a host cavity and a monomer arrangement may yield new stereoregular polymers.…”

Section: Resultsmentioning

confidence: 99%

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

Inoue

Katō

Tohnai

et al. 2004

J. Polym. Sci. A Polym. Chem.

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We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 21‐helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close‐packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2‐methyl‐trans‐1,3‐pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004

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“…If the trienes also are aligned with a tilt angle of about 29°, the reacting carbon atoms (C1-C6) of adjacent p-systems will approach each other to within a close contact (3.5 Å). Since these supramolecular structural features are very similar to those previously used for the triacetylene polymerization, Lauher and Fowler et al decided again to explore the same strategy for a 1,6-triene polymerization [67]. This approach involves the use of two molecules; one acts as the host, controlling the supramolecular structure and establishing the 7.2 Å translational repeat distance, and the other, the guest, is the intended triene monomer.…”

Section: Topochemical Polymerization Of Other Monomersmentioning

confidence: 94%

“…One of the intended triene guest molecules, shown in Scheme 10, was prepared and its crystal structure revealed a supramolecular structure that might Scheme 10 Topochemical 1,6-polymerization of a triene [67] be suitable for a topochemical polymerization. When the single crystal was heated to 110°C for 8 h, this process resulted in a smooth transformation to a new material whose X-ray crystal structure clearly demonstrated that a topochemical 1,6-polymerization of the triene to a polytriene had occurred.Although the polymerization of the triene was a serendipitous discovery, it clearly demonstrates that the topochemical polymerization of a triene is possible, thus adding it to the small but growing number of important topochemical reactions.…”

Section: Topochemical Polymerization Of Other Monomersmentioning

confidence: 99%

Reactions of 1,3-Diene Compounds in the Crystalline State

Matsumoto

2005

Organic Solid State Reactions

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The Topochemical 1,6-Polymerization of a Triene

Cited by 103 publications

References 10 publications

Polymer Structure Control Based on Crystal Engineering for Materials Design

Polymer Structure Control Based on Crystal Engineering for Materials Design

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

Reactions of 1,3-Diene Compounds in the Crystalline State

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