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

Matsumoto, Akikazu

doi:10.1007/b101001

Cited by 70 publications

(6 citation statements)

References 95 publications

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“…( Wang et al., 2015a ) Thus, it was necessary to alter its structure using crystal engineering. ( Biradha and Santra, 2013 ; d'Agostino et al., 2016 ; Kole et al., 2015 ; Matsumoto, 2005 ; Matsumoto et al., 2000 ; Tsaggeos et al., 2012 ) According to Schmidt’s topochemical principles, in order for two C=C bonds to react via [2 + 2] photocycloaddition in the solid state, they need to be parallel and less than 4.2 Å apart. ( Schmidt, 1971 ) To this end, a 2:1 salt of sorbic acid and ethylenediamine was prepared by growing crystals from an ethanol solution ( Figure 2 ).…”

Section: Resultsmentioning

confidence: 99%

A biorenewable cyclobutane-containing building block synthesized from sorbic acid using photoenergy

et al. 2022

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Section: Resultsmentioning

confidence: 99%

A biorenewable cyclobutane-containing building block synthesized from sorbic acid using photoenergy

et al. 2022

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“…Therefore, to successfully photo-cross-link the fibrils in the self-assembled state, the photopolymerizable group should not only be able to traverse across this distance but also maintain this separation after the photo-cross-linking reaction without distorting the peptide secondary structure. In this regard, 1,3-diynes and 1,3-dienes , are ideal since successful topochemical polymerization has been shown to occur when their respective functionalities are aligned at a distance of 4.9−5.1 Å in the crystalline state. Importantly, this distance is maintained throughout the photopolymerization process.…”

Section: Resultsmentioning

confidence: 99%

De Novo Design of a Shear-Thin Recoverable Peptide-Based Hydrogel Capable of Intrafibrillar Photopolymerization

2010

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A de novo designed peptide-based gel has been prepared whose mechanical rigidity can be modulated after shear-thin recovery. The photopolymerizable β-hairpin peptide named MLD undergoes temperature-induced folding and self-assembly to afford a network of β-sheet-rich fibrils that constitutes a moderately rigid hydrogel (G 0 = 220 ( 50 Pa, 1 wt %). The MLD hydrogel can be shear-thinned into a lowviscosity gel upon application of shear stress and immediately recovers its mechanical rigidity upon termination of stress. MLD peptides contain non-natural sorbamide derivatives of lysine that allow the mechanical rigidity of its hydrogels to be enhanced through polymerization of dienes displayed along the surface of the fibrils constituting the gel. Irradiation of the gel network increases its mechanical rigidity ∼2.5-fold. Circular dichroism (CD) spectroscopy shows that MLD folds and self-assembles into β-sheet-rich fibrils and that photo-cross-linking does not influence the secondary structure contained within the assembly. The MLD hydrogel shows potential as an injectable material whose mechanical properties can be modulated after delivery.

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“…Among various π-conjugated polymers, polydiacetylenes (PDAs) are quite unique in their preparation process, i.e., topochemical polymerization of butadiyne derivatives . Except for butadiyne derivatives, limited monomers can be polymerized in the solid state, e.g., compounds with two CC bonds to show [2 + 2] photocycloaddition reactions, − butadienes, − hexatriene, hexatriyne, and quinodimethanes. − In the crystals, all these monomers should take the proper polymerizable arrangement in which distances between intermolecular reacting atoms are within the mobile ranges, and the case of butadiynes is as well. As shown in Figure , the appropriate conditions of the monomer arrangement for the polymerization have been reported as follows: The distance d between two adjacent butadiyne monomers along the translation direction, i.e., the polymerization direction, is about 5 Å, and the angle θ between the translation direction and the linear butadiyne moiety is about 45°. , As materials for electronics and photonics, control of the electronic state is an important issue, and introduction of conjugated substituents is one of the general strategies.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structures, and Solid-State Polymerization of 8-[4-(Dimethylamino)phenyl]octa-5,7-diynyl Carbamates

Ikeshima

Katagiri

Fujiwara

et al. 2018

Crystal Growth & Design

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Six butadiyne monomers with (dimethylamino)phenyl and N-substituted urethane substituents were synthesized and their crystal structures and solid-state polymerization were investigated. In five of the six monomers, directions of the butadiyne stacking and the intermolecular hydrogen bonding between urethane groups coincided, and translational distance d between adjacent butadiyne moieties was around 5 Å. Among them, four monomers showed angle θ between the translation axis of the monomers and the butadiyne moiety of around 45°, which is appropriated for regular 1,4-addition polymerization. These geometries resulted in formation of polydiacetylenes with characteristic excitonic absorption and relatively high conversion. One monomer was found to have large θ, and the regular polymerization was not recognized to be quite low conversion. However, in the remaining one monomer among six, the directions of butadiyne stacking and intermolecular hydrogen bonding were different and d was much longer than 5 Å. However, distance between reacting carbons for 1,4-addition was short enough resulting in comparable conversion without regular polymerization. Although introduction of urethane group is effective to increase probability of the solid-state polymerization of butadiynes, hydrogen bonding direction, methylene chain conformation, and disorder of the aromatic rings were found to afford the variation from the appropriate conditions.

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

Cited by 70 publications

References 95 publications

A biorenewable cyclobutane-containing building block synthesized from sorbic acid using photoenergy

A biorenewable cyclobutane-containing building block synthesized from sorbic acid using photoenergy

De Novo Design of a Shear-Thin Recoverable Peptide-Based Hydrogel Capable of Intrafibrillar Photopolymerization

Synthesis, Crystal Structures, and Solid-State Polymerization of 8-[4-(Dimethylamino)phenyl]octa-5,7-diynyl Carbamates

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