Novel polydiacetylenes for optical materials: beyond the conventional polydiacetylenes

Sarkar, Abhijit; Okada, Shuji; Matsuzawa, Hiroshi; Matsuda, Hiro; Nakanishi, Hachiro

doi:10.1039/a907438d

Cited by 137 publications

(103 citation statements)

References 30 publications

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“…Since the oily compound 9 has a high reactivity in its pure state, it was stored in solution. Spectroscopic data for 9 were as follows: 1 H-NMR (270 MHz, CDCl 3 ) d 1.29-1.40 (10 H, m), 1.50-1.58 (4H, m), 2.04 (1H, s), 2.29 (2H, t, J¼7.1Hz), 3.64 (2H, t, J¼6.6 Hz), the protons of the hydroxyl groups were not clearly detected; 13 …”

Section: Synthesis Of Monomersmentioning

confidence: 96%

“…Isopropylamine (30 ml) and copper(I) chloride (82 mg) were added to a solution of 7 (0.76 g, 4.00 mmol) in methanol (5 ml) under a nitrogen atmosphere at ambient temperature. After stirring for 5 min, 4-bromo-2-methyl-3-butyn-2-ol 5 (1.04 g, 6.40 mmol) was added dropwise to the solution for 2 h. The further experimental procedure was exactly the same as the synthesis of 6, and 0.39 g of 8 (36%) was obtained as a white powder: 1 H-NMR (270 MHz, CDCl 3 ) d 1.28-1.59 (14H, m), 1.54 (6H, s), 2.30 (2H, t, J¼7.1 Hz), 3.56 (2H, t, J¼6.6 Hz), the protons of the hydroxyl groups were not clearly detected; 13 10,12,14-Pentadecatriyn-1-ol 9. Powdered potassium hydroxide (0.16 g, 2.80 mmol) was added to a solution of 8 (0.38 g, 1.40 mmol) in toluene (23 ml), and the mixture was heated at 80 1C for 2 h. After filtration of the mixture, the filtrate was concentrated under reduced pressure.…”

Section: Synthesis Of Monomersmentioning

confidence: 99%

“…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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confidence: 99%

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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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Section: Synthesis Of Monomersmentioning

confidence: 96%

Section: Synthesis Of Monomersmentioning

confidence: 99%

mentioning

confidence: 99%

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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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“…The study of conjugated organic oligomers with specific π−delocalization patterns can also provide the basis for the realization of useful polymer-based materials by using trends in the molecular properties to model those of the polymer system. Many linearly conjugated oligomers have been explored as advanced materials, including those based on a framework of poly(phenylene ethynylene), 2 polydiacetylene, 3 and polytriacetylene. 4 An alternative conjugation motif, namely cross conjugation, is also of interest in constructing oligomeric systems.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of cross-conjugated oligo(phenylene enynylene)s

Cho¹,

Zhao²,

Tykwinski³

2005

Arkivoc

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The synthesis and characterization of a series of cross-conjugated oligo(phenylene enynylene)s via the Sonogashira protocol is reported. The structural properties of these oligomers have been established by 1 H and 13 C NMR and IR spectroscopies, as well as mass spectrometry. Their electronic absorption and emission behavior has been investigated via UV/Vis and fluorescence spectroscopy. The results of this study demonstrate that electronic communication along the conjugated framework of these oligomers is limited due to the presence of a cross-conjugated enyne framework and arylene fragments.

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“…-Diacetylenes (DAs, i.e., butadiynes) are an important class of compounds that can be converted into functional materials such as polydiacetylenes (PDAs) for third-order nonlinear optical devices [1], thiophene derivatives for organic light-emitting devices [2], and oligoenes/oligoynes for molecular wires [3]. Pyridinium salts have attracted considerable attention because of their applications in cationic surfactants [4], nonlinear optical materials [5], phase-transfer catalysts [6], and also as initiators of cationic polymerization [7].…”

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confidence: 99%

Synthesis and Chemical Properties of Diacetylenes with Pyridinium and 4,4′‐Bipyridinium Groups

Yamaguchi

Higashi

Kimura

et al. 2010

Helvetica Chimica Acta

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Diacetylenes (DAs) having a dipolar D‐π‐A structure (D=donor: amino group; π=π‐conjugation core; A=acceptor: pyridinium (Py) and bipyridinium (BPy) groups), i.e., 4 (APBPyDA) and 5 (APPyPyDA), or an A‐π‐A structure, i.e., 7 (DBPyDA) and 8 (PyDA(Cl)), were obtained by 1 : 1 and 1 : 2 reactions of 4,4′‐(buta‐1,3‐diyne‐1,4‐diyl)bis[benzenamine] (APDA; 3) with 1‐(2,4‐dinitrophenyl)‐1′‐hexyl‐4,4′‐bipyridinium bromide chloride (1 : 1 : 1) (1), 1‐(2,4‐dinitrophenyl)‐4‐(pyridin‐4‐yl)pyridinium chloride (2), or 1‐(2,4‐dinitrophenyl)pyridinium chloride (6) (Schemes 1 and 2). The anion‐exchange reactions of 8 with NaI and Li(TCNQ) (TCNQ−=2,2′‐(cyclohexa‐2,5‐diene‐1,4‐diylidene)bis[propanedinitrile] radical ion (1−)) yielded the corresponding I− and TCNQ− salts 9 (PyDA(I)) and 10 (PyDA(TCNQ)). Compounds 10 and 4 exhibited a UV/VIS absorption due to a charge transfer between the TCNQ− and the pyridinium groups and a strong solute–solvent interaction of a dipolar solute molecule in the polar environment, respectively. Compounds 8–10 exhibited photoluminescence in solution, whereas 4 and 7 did not because of the presence of the 4,4′‐bipyridinium quenching groups. Differential‐scanning‐calorimetry (DSC) measurements suggested that the DAs obtained in this study can be converted into poly(diacetylenes) by thermal polymerization.

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Novel polydiacetylenes for optical materials: beyond the conventional polydiacetylenes

Cited by 137 publications

References 30 publications

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

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

Synthesis and characterization of cross-conjugated oligo(phenylene enynylene)s

Synthesis and Chemical Properties of Diacetylenes with Pyridinium and 4,4′‐Bipyridinium Groups

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