Diacetylene Derivatives Research Articles

Reversible Color Changes of Polydiacetylene Induced by Monomer Solid Phase Transition

Abstract Color change associated with solid phase transition is observed in the diacetylene derivatives, partially polymerized 4,6-decadiyne-1,10-bis(propylurethane). Moreover, the temperature of this color change can be altered by mixing with other derivatives.

Polymerization of Chemically Adsorbed Monolayer of Diacetylene Derivatives initiated by UV or EB Irradiation.

Polymerization of Chemically Adsorbed Monolayer of Diacetylene Derivatives initiated by UV or EB Irradiation.

Photopolymerization of monomolecular films with diacetylene bonds on an aqueous subphase

The photoreactivity of monomolecular films of a diacetylene derivative (10,12-pentacosadiynoic acid (PDA)) under UV irradiation has been investigated at the air-water interface. With decreasing molecular area, the reactivity of the Langmuir film (the Langmuir film is the monomolecular film on an aqueous subphase) decreased, and the colour transition of the Langmuir film polymerized by the UV irradiation was from blue to red. Furthermore, the colour transition (blue to red) was also caused by heating the polymerized Langmuir-Blodgett (LB) films at about 60°C. The colour transition of the polymerized PDA Langmuir film exhibited reversibility at the air-water interface when the condition of the subphase was changed, but that of the LB films did not exhibit reversibility. In the differential scanning calorimetry diagrams, the PDA LB films had an endothermal peak a 67°C, but the polymerized film had two peaks at about 70 and 200°C. These results indicate that the photoreactivity of the PDA monomolecular film at the air-water interface was affected by the molecular arrangement and density, and the colour transition of the PDA polymer may be caused by the structural disorder of the side-groups joined to the polymer backbone.

Studies on Langmuir-Blodgett films fabricated from the monolayers containing polydiacetylene and polythiophene derivatives

A stable mixed monolayer, composed of a soluble conducting polymer, poly(3- hexylthiophene) (PHT), and a topochemically polymerizable amphiphilic diacetylene derivative, pentacosa-10, 12-diynoic acid (DA), was formed on an aqueous subphase. The structure of the deposited Langmuir-Blodgett (LB) films has been investigated by X-ray diffraction and second harmonic generation. It has been shown that the LB films have a well-defined layered structure, which is considered to contain partly a double-layered structure of PHT and DA. The PHT chain is well oriented in the LB films, so that its total dipole moment is perpendicular to the substrate when the ratio of PHT repeating unit to DA is less than unity.

ChemInform Abstract: Syntheses of Diacetylenic Derivatives with Mesogenic Group.

AbstractThe hexadiynediol (I) reacts with the acid chlorides (II) and (IV) to give the diesters (III) and (V).

Acetylenic and diacetylenic liquid-crystalline monomers: towards ordered conjugated polymers

Abstract Acetylenic and diacetylenic mesomorphic monomers have been prepared in order to obtain long conjugated polymers able to give high non-linear optical hyperpolarizabilities. Here we report the synthesis of such monomers incorporating cholesteryl and methoxybiphenyl groups; their structural and thermal behaviour are described. The occurrence of mesophases in the acetylenic and diacetylenic derivatives is discussed as a function of the spacer length and of the size of the mesogen moiety. The diacetylenic derivatives containing the methoxybiphenyl groups do not exhibit any liquid-crystalline behaviour but are able to polymerize under U.V. radiation.

ChemInform Abstract: Synthesis and Solid‐State Polymerization Properties of Symmetrical and Unsymmetrical Diacetylene Derivatives Containing a ′Polymerogenic′ Side Group.

AbstractThe hexadiynediol (I) reacts with benzyl isocyanate (II) to give the carbamates (IIIa) and (IIIb).

Photopolymerization in monolayers of an amphiphilic diacetylene derivative containing a ferrocene group

The photopolymerization of heptadeca-2,4-diynylferrocenecarboxylate in the monolayer on a water surface was investigated by studying pressure–area isotherms and electronic spectra; the polymerization behaviour was found to depend markedly on the molecular packing in the monolayer.

Synthesis and solid-state polymerization properties of symmetrical and unsymmetrical diacetylene derivatives containing a ‘polymerogenic’ side group

The ability of a benzyl urethane side group (R1O) to promote the solid-state polymerization of diacetylenes R1OCH2–CC–CC–CH2OR2 has been demonstrated on the basis of chemical and X-ray structural data.

Surface properties of a long-chain 10:12 diynoic acid monolayer at air-liquid and solid-liquid interfaces

Monolayer stabilities of two long-chain diacetylene monocarboxylic acids at fluid interfaces have been studied and are compared with those of a conventional n-alkanoic acid. The diacetylene derivatives form highly incompressible solid monolayers at the air-liquid interface. Their surface pressure-area isotherms are shown to depend on the mode of monolayer compression, indicating the necessity of a cautious approach to experimental protocol. The coherence of deposited monolayers on hydrophobic glass surfaces was characterized by interference reflection microscopy. Birefringent crystals were obtained with UV polymerized pentacosanoyl 10:12 diynoic acid in sharp contrast to the well-defined deposition behaviour observed for monolayers of eicosanoic acid.

Synthesis and polymerization of 6‐(p‐toluenesulfonyloxy)‐2,4‐hexadiynyl p‐fluorobenzenesulfonate, an asymmetrical diacetylene derivative. X‐ray crystal structures of the monomer and of the polymer at 143 K

Die Makromolekulare Chemie, Rapid CommunicationsVolume 8, Issue 9 p. 443-450 Article Synthesis and polymerization of 6-(p-toluenesulfonyloxy)-2,4-hexadiynyl p-fluorobenzenesulfonate, an asymmetrical diacetylene derivative. X-ray crystal structures of the monomer and of the polymer at 143 K Marcel Bertault, Corresponding Author Marcel Bertault Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, France Marcel Bertault, Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, France André Collet, Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, FranceSearch for more papers by this authorLoïc Toupet, Loïc Toupet Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, FranceSearch for more papers by this authorJosette Canceill, Josette Canceill Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, FranceSearch for more papers by this authorAndré Collet, Corresponding Author André Collet Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, France Marcel Bertault, Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, France André Collet, Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, FranceSearch for more papers by this author Marcel Bertault, Corresponding Author Marcel Bertault Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, France Marcel Bertault, Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, France André Collet, Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, FranceSearch for more papers by this authorLoïc Toupet, Loïc Toupet Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, FranceSearch for more papers by this authorJosette Canceill, Josette Canceill Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, FranceSearch for more papers by this authorAndré Collet, Corresponding Author André Collet Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, France Marcel Bertault, Laboratoire de Physique cristalline, U.A. 804 du C.N.R.S., Université de Rennes I, Campus de Beaulieu, 35042 Rennes cedex, France André Collet, Chimie des Interactions moléculaires, E.R. 285 du C.N.R.S., Collège de France, 11, place Marcelin-Berthelot, 75005 Paris, FranceSearch for more papers by this author First published: September 1987 https://doi.org/10.1002/marc.1987.030080905Citations: 15AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Citing Literature Volume8, Issue9September 1987Pages 443-450 RelatedInformation

Liquid crystals for non-linear optics: mesophases formed by push–pull stilbenes and diacetylenes

The push–pull stilbene and diacetylene derivatives (1f–h) and (2c–k) display nematic and smectic phases, which may be of special interest for their non-linear optical properties.

The crystal and molecular structure of an asymmetric diacetylene monomer, 6‐(4‐dimethylaminobenzoyloxy)‐2,4‐hexadiynyl 3,5‐dinitrobenzoate

AbstractThe crystal and molecular structure of an asymmetric diacetylene derivative, 6‐(4‐dimethylaminobenzoyloxy)‐2,4‐hexadiynyl 3,5‐dinitrobenzoate (1), was determined from x‐ray diffraction data. The crystals are monoclinic, P21/c with Z = 4 in a unit cell having dimensions, a = 11,116 (1) Å, b = 13,429 (2) Å, c = 14,672 (3) Å, β = 106,84 (6)°. The structure was solved by direct methods and refined by least‐squares techniques to an RF of 6,2% for 1 991 independent reflections. The diacetylene backbone chains are almost perfectly parallel to the ac‐plane; however, they are displaced from each other in the [010] direction. The solid‐state polymerization mechanism is discussed with respect to the geometric disposition of the diacetylene chains, which in this crystal are too far apart to permit polymerization by means of 1,4‐addition, consistent with the Baughman mechanistic model.

Syntheses and polymerization of diacetylene derivatives containing α,ω‐di‐β‐naphthyloxy groups

Syntheses and polymerization of diacetylene derivatives containing α,ω‐di‐β‐naphthyloxy groups

ChemInform Abstract: SYNTHESIS OF MONO‐ AND DIACETYLENIC DERIVATIVES OF SILYLFERROCENE

Chemischer InformationsdienstVolume 16, Issue 2 Organoelement Compounds ChemInform Abstract: SYNTHESIS OF MONO- AND DIACETYLENIC DERIVATIVES OF SILYLFERROCENE A.-G. A. EL-AGAMEY, A.-G. A. EL-AGAMEYSearch for more papers by this authorL. P. ASATIANI, L. P. ASATIANISearch for more papers by this author A.-G. A. EL-AGAMEY, A.-G. A. EL-AGAMEYSearch for more papers by this authorL. P. ASATIANI, L. P. ASATIANISearch for more papers by this author First published: January 15, 1985 https://doi.org/10.1002/chin.198502303AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume16, Issue2January 15, 1985 RelatedInformation

Calculations of induced moments in large molecules. The average polarisability and second hyperpolarisability of some polyacetylenes and a scale of polarisation for CH3, F, H and NH2. A comparative study

The average polarisability, α, and second hyperpolarisability, γ, of H2(C2)n, where n= 1–8, are reported. The dipole interaction theory has been invoked for the rationalisation of these results. The effective polarisabilities and hyperpolarisabilities of CH3, F and NH2 with respect to H have been investigated in some acetylene and diacetylene derivatives. The established order for the effective polarisabilities is F < H < NH2 < CH3, while F < H < CH3 < NH2 has been found for the effective second hyperpolarisabilities. The proposed relationships have been confirmed in a further series of molecules representative of substituted alkanes, alkenes and arenes. The computations have been performed by employing the CHF–PT–EB–CNDO method, the reliability of which is well established.

Structure of a ‘doped’ diacetylene that is polymerisable in the solid state

The crystal structure has been determined of a silver perchlorate-doped diacetylene derivative which yields upon γ-ray irradiation a semi-conducting polymer product; whereas the perchlorate ions are randomly distributed throughout the monomer structure, the silver ions are preferentially located close to the electron rich regions of the organic molecular framework.

Diacetylene alcohol derivatives of aromatic amines

We have developed methods of synthesis of acetylenic and diacetylenic alcohol derivatives of simple aromatic amines.

Synthesis of mono- and diacetylenic derivatives of silylferrocene

1-Ferrocenyl(methyl)phenylsilane (I) was prepared by silylation of ferrocene at low temperature. Mono- and diacetylenic compounds of silyferrocene were prepared by the interaction of chloroferrocenylsilane with mono- and dilithium acetylenic derivatives, respectively. It has been found that, catalytic hydrogenation of the prepared acetylenic compounds seem to be totally determined by steric considerations.

Solid State Chemistry of Some Diacetylenic Acid Derivatives

Abstract An example of chemical reactivity in LB films is described, α and ω diyne long chain fatty acids are synthetized and their polymerization in multilayers studied. The reactivity depends on the position of the diyne along the alkylchain and on the metallic ion so far as the α diyonic acid salt is concerned. In LB films the chemical reactions are followed by infrared spectroscopy and the spectra are compared to those of model synthetic analyzed compounds. Decarboxylation often takes place under UV radiation or heat and leads to unpolymerisable material. From an oxidative coupling of the copper salt a tetrayne formation is presumed and a fast polymerization under visible radiation is observed