Structure of 3,5-octadiyne-1,8-diol at 120 K

Fisher, Dorothea.; Ando, David; Batchelder, D. N.; Hursthouse, M. B.

doi:10.1107/s0567740878012261

Cited by 9 publications

(4 citation statements)

References 6 publications

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“…28 Similar is the case for R-CtC-CtC-R [R ) -CH 2 -CH 2 -OH]. 29 For 3BCMU, an explanation that has been proposed is that, in the crystal, the molecules are held together by strong H-bonds and thermal activation is not enough to overcome these strong interactions and hence is thermally inactive. On the other hand, in photopolymerization and radiation polymerization enough energy is available to initiate the reaction, the crystal packing being quite suitable for reaction.…”

Section: Resultsmentioning

confidence: 90%

“…For example, the diacetylene 3BCMU [R = −(CH 2 )−OCONH−CH 2 −COO(CH 2 ) 3 CH 3 ] can be polymerized by γ-radiation, but it is unreactive when heat is used . Similar is the case for R−C⋮C−C⋮C−R [R = −CH 2 −CH 2 −OH] . For 3BCMU, an explanation that has been proposed is that, in the crystal, the molecules are held together by strong H-bonds and thermal activation is not enough to overcome these strong interactions and hence is thermally inactive.…”

Section: Resultsmentioning

confidence: 97%

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Polydiacetylenes from Asymmetrically Substituted Diacetylenes Containing Heteroaryl Side Groups for Third-Order Nonlinear Optical Properties

et al. 1998

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Synthesis of a series of asymmetrically substituted diacetylenes containing a thienyl moiety or a quinolyl moiety as one of the side groups directly bound to diacetylene and a urethane group as the other one was carried out. Though some of the prepared diacetylenes could be polymerized in solid state by using UV and γ-radiation, all of them were stable when heat was used as the stimulus. The monomer to polymer conversion for the polymerizable ones was found to be in the range 35−60%. Various spectroscopic techniques, such as FTIR, solid state 13C NMR and visible absorption spectroscopies, and powder X-ray diffraction were used to elucidate the structures of the polydiacetylenes. One of the polymers containing quinolyl moiety as directly bound side group showed unusually long and sharp absorption maximum indicating long and uniform conjugated chains. Third-order nonlinear optical susceptibility, χ(3), of two of the polymers were measured using Maker's fringe technique. The largest value for χ(3) in the resonant region for polymer backbone direction in single crystalline form was estimated to be on the order of 10-11 esu.

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 97%

Polydiacetylenes from Asymmetrically Substituted Diacetylenes Containing Heteroaryl Side Groups for Third-Order Nonlinear Optical Properties

et al. 1998

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“…However, intermolecular hydrogen bonding between hydroxyl groups is often observed across adjacent two molecular arrays. 31,32 This type of network interaction may increase the disorder in crystals during two-step polymerization because disorder in one molecular array causes disorder in the adjacent two molecular arrays. This is one of the plausible explanations for the polymerization behavior of 1, which shows regular polymerization in the first step and disordered polymerization in the second step.…”

Section: Resultsmentioning

confidence: 99%

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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“…The unsubstituted monomer is predicted to react most favorably toward polymerization. Experimentally, it is known that the diol monomer is reactive in the solid state and that the ditosylate is known to react over time in the solid state even in the dark . Both the diphenyl and diketal series are relatively stable to polymerization. , Unsubstituted DA is a gas and has not been studied in solution or solid state where close contact of monomer units allow verification of the monomer's reactivity at standard temperature …”

Section: Resultsmentioning

confidence: 99%

Theoretical Studies of a Highly Reactive Diacetylene Monomer, 3,5-Octadiyn-2,7-dione, and Its Cross-Conjugated PDA Oligomers

1996

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Polydiacetylene derivatives have great potential in the area of nonlinear optics. Several factors affect the usefulness of these materials, and it is desirable to model the effects of these factors before time and resources are spent in the development of new materials. Our work focuses on a particular derivative, 3,5-octadiyn-2,7-dione, ODDO, which related work has shown to be highly polymerizable in solution. The interesting polymer poly-ODDO has acetyl groups cross-conjugated with the conjugated backbone. Calculations show that the monomer's reactivity may be partially explained on thermodynamic grounds. The utility of the AM1 method in MOPAC 6.0 as a model for PDA experimental optical properties is shown. Conformers of ODDO and its oligomers are calculated at high precision using AM1 to see the variation in optical properties and stability as a function of backbone planarity and substituent alignment relative to the backbone, in an effort to determine whether or not there would be any benefit in optical properties to attempts to control the conformation. Analysis of the data indicates that backbone planarity should be important to optical properties, as one would expect, and that substituent orientation has much less effect than one might expect from a cross-conjugated substituent. Specific coplanar orientations are predicted to have a large relative effect on stability but only a minor effect on optical properties. Coplanar ODDO oligomers are predicted to have lower HOMO-LUMO gaps and better third-order nonlinear optical properties than equivalent unsubstituted oligomers. The data also show that monomeric HOMO-LUMO gaps may not reliably predict the relative utility of polymeric nonlinear optical materials.

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Structure of 3,5-octadiyne-1,8-diol at 120 K

Abstract: Abstract. OHH2C-H2C-C--C-C-C--CHThe structure was refined to R = 0.042 for 1016 counter reflections. The crystal structure accounts for the observed solid-state reactivity of 3,5-octadiyne-1,8-diol.

Cited by 9 publications

References 6 publications

Polydiacetylenes from Asymmetrically Substituted Diacetylenes Containing Heteroaryl Side Groups for Third-Order Nonlinear Optical Properties

Polydiacetylenes from Asymmetrically Substituted Diacetylenes Containing Heteroaryl Side Groups for Third-Order Nonlinear Optical Properties

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

Theoretical Studies of a Highly Reactive Diacetylene Monomer, 3,5-Octadiyn-2,7-dione, and Its Cross-Conjugated PDA Oligomers

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