Synthesis and solid-state polymerization of diacetylene derivatives directly substituted with a phenylcarbazole moiety

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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.

Section: ■ Results and Discussionsupporting

confidence: 89%

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

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“…The PDAs are not only pH- and thermochromic but also photo-, mechano-, and radiochromic, , dominated by a transition between a nonemissive form, sometimes called the “blue” form, and a fluorescent state (“red” form) . Applications such as organic electronics, − biosensors, , paper sensors, bioimaging, , and delivery of drugs or biomolecules have also been developed, but the major area of applications is the detection of chemicals such as volatile organic compounds and biorelated species such as bacteria , and viruses. , More recently, major advances have been made in the field of food biotechnology and security. , Although the importance of incorporating functional side arms to the conjugated backbone was clearly stressed, − surprisingly, the use of chiral groups has attracted only a modest attention. − It is noteworthy that chiral pendants can act as functional groups in PDAs, but interestingly, they can also act as supramolecular units programming specific preferential packing arrangements in the crystalline state prior to photopolymerization of the diacetylene (DA) monomers. To the best of our knowledge, this latter important application appears to be relatively neglected.…”

Section: Introductionmentioning

confidence: 99%

Selective Chirality-Driven Photopolymerization of Diacetylene Crystals

Baillargeon,

Boivin,

Vaillancourt

et al. 2024

Crystal engineering of two diacetylene monomers was achieved by branching two chiral groups [R = PhC*MeNH(CO2)CH2] exhibiting an enantiopure configuration of S,S-(DA2) and an achiral R,S-meso-isomer (DA4). The X-ray structures of DA2 and DA4 reveal the presence of supramolecular arrangements driven by intermolecular H-bonding. A significant intermolecular closer proximity in DA4 than that in DA2 is depicted, ultimately resulting in a slow thermal (days) and swift (min) photochemical polymerization of DA4 to form PDA5, whereas DA2 is unreactive. DFT computations indicate that in both cases the lowest energy-excited state is the charge-transfer state [CT; PhC*MeNH(CO2) → π*(−CC–CC−)]. Therefore, this outcome illustrates a drastic selectivity via a settle change in a carbon configuration. Analysis demonstrates that PDA5 is nonemissive and that its coloration arises from a π → π* excitation of the polymer backbone (DFT computations).

“…One of the strategies is to use a supramolecular host–guest system. , The other is modification by specific groups, which tend to align monomers in one-dimensional (1D) arrays. We have used the latter strategy to prepare butadiyne monomers with π conjugation between the backbone and substituents. , For example, butadiyne derivatives directly bound to electron-donating aromatics such as pyrene, , N -phenylcarbazole, , aniline, , and tetrathiafluvalene (TTF) were recently synthesized, and some of them polymerized regularly to form PDAs with conjugated donors. Meanwhile, in order to improve the PDA processability, one of the potential approaches is its solubilization.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Solid-State Polymerization of 5-(Pyren-1-yl)penta-2,4-diyn-1-ol Derivatives with an N-Phenylurethane or N-Benzylurethane Group

Oshimizu

Takeshi

Sato

et al. 2020

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A series of 5-(pyren-1-yl)penta-2,4-diyn-1-yl N-phenylcarbamates and N-benzylcarbamates were synthesized. Phenyl groups in the N-phenyl and N-benzyl moieties were unsubstituted (H-0 and H-1, respectively) and 3,4,5-trialkoxy substituted (C m O-0 and C m O-1, respectively), in which the alkyl groups introduced were methyl (m = 1), octyl (m = 8), dodecyl (m = 12), and hexadecyl (m = 16) groups. Upon UV irradiation, a regular 1,4-addition polymerization to form polydiacetylene was confirmed for H-0, H-1, C 8 O-1, C 12 O-1, and C 16 O-1. For C 1 O-0 and C 1 O-1, the crystal structures were solved, and the reasons the regular polymerization did not occur were clarified. From the powder X-ray diffraction study, crystallinities of C m O-1 were found to be lower than those of C m O-0, although C m O-1 regularly polymerized. This indicates that the total crystallinity is not directly related to local ordering around one-dimensional arrays for the polymerization direction. Polymerized C m O-1 species were soluble in chloroform. Their processability enabled us to fabricate cast films of polydiacetylene as well as the monomer. The conductivities of C 12 O-1 and the polymer (PC 12 O-1) were evaluated in the pristine and iodine-doped states and in the charge-transfer-complexed states with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. A conductivity of 1.2 × 10 −2 S m −1 for iodine-doped PC 12 O-1 was achieved. In this case, pyrene moieties seemed to play an important role in realizing the appropriate electron transfer from pyrene moieties to iodine molecules and effective π conjugation between the pyrene moieties and the PDA backbone promoting charge transport.