Diacetylene Derivatives Research Articles

Crystal structure of aromatic diacetylene derivatives and reactivity of solid-state polymerization

Crystal structure of aromatic diacetylene derivatives and reactivity of solid-state polymerization

Bimane Acetylenes and Diacetylenes. Bimanes. 33

Two series (4,6-dihydro and 4,6-dimethyl) of syn-bimanes [1,5-diazabicyclo[3.3.0]octa-3,6-diene-2,8-diones] have been converted to acetylene and diacetylene derivatives. Their chemical and photophysical properties are reported. The 3-(and 6-)iodo (diiodo) derivatives are the best choices for Stille or Heck condensations with acetylenes or acrylates. Desilylation of (trimethylsilyl)acetylenes is best carried out with silver nitrate followed by lithium bromide. The acetylenes and diacetylenes are quite stable and highly fluorescent and represent candidate units for incorporation into polymers.

Infrared and Resonance Raman Spectroscopic Study on the Photopolymerization Process of the Langmuir−Blodgett Films of a Diacetylene Monocarboxylic Acid, 10,12-Pentacosadiynoic Acid

Absorption, infrared reflection absorption (IRA), and resonance Raman scattering (RRS) spectroscopies were applied to obtain direct information about the conformation change of a polydiacetylene (abbreviated to PDA) produced by UV irradiation of the Langmuir−Blodgett (LB) films of the cadmium salt of a diacetylene derivative, 10,12-pentacosadiynoic acid (DA), with the number of monolayers from 1 to 31. The rate and extent of the polymerization of DA monitored by the relative intensity change of the IRA bands due to C⋮C stretching vibrations were correlated with orientation changes of the alkyl groups of DA and changes in the conjugation length of the PDA backbone elucidated by RRS spectra in the C⋮C stretching vibration region. The results proved the following mechanism of the conversion from a blue (λmax ≈ 635 nm) to a red phase (λmax ≈ 540 nm) during the polymerization of DA. The conversion proceeds through two steps. The polymerization reaction itself is almost completed in the first step, although a r...

Spectroscopic studies on aggregation of squarylium dyes and the photopolymerization of a diacetylenic derivative in monolayers at the air/water interface

Molecular orientation and aggregation forms of squarylium dyes and also photopolymerization of an amphiphilic diacetylene derivative containing ferrocene, namely heptadeca-2,4-diynylferrocene carboxylate (FcDA), in monolayers at the air/water interface have been investigated by measurements of UV-visible spectra in situ. The aggregation forms of the dyes in the monolayers can be controlled by altering the position and the length of the substituted alkyl chains, as well as by changing the subphase temperature and the surface pressure. Two types of J-aggregates were obtained with bis(dipropylaminophenyl)squarylium dye, depending on the pressure and the temperature, while almost pure H-aggregate could be obtained with bis(dibutylaminophenyl)squarylium dye under high compression at 20°C. Further, the polymerization of FcDA together with the resultant polymer structure are significantly influenced by the orientation and packing of the monomer molecules in the monolayer. Suitably close packing with ordered arrangements of the monomer molecules at higher pressure and lower temperature produced the blue form of the polymer, while rather loosely packed monomer molecules with some conformational freedom at lower pressure and higher temperature gave the red form of the polymer.

Structure of Self-Assembled Monolayers from Amphiphilic Diacetylene Derivatives on Indium-Tin Oxide

Self-assembled monolayers (SAMs) of amphiphilic diacetylene derivatives CH3(CH2)n C≡C-C≡C(CH2)8COOH (n=9, 11, 13, 15) were prepared on an indium-tin oxide (ITO)/glass substrate by chemisorption from the solution. Infrared transmission spectra, visible transmission spectra, and contact angles of water revealed that the SAMs of the diacetylenes are sparse monolayers on the substrate, while the Langmuir-Blodgett monolayer is a condensed one: density of the molecules on the SAMs was approximately estimated to be one molecule/nm2.

Polymerization of 10,12‐docosadiyne‐1,22‐ disulfate in self‐assembled multilayers

The polymerization of diacetylenes in self‐assembled multilayers (see Figure) should lead to a new type of ultrathin films exhibiting interesting optical and electronic properties. Here the preparation of water‐soluble diacetylene derivatives, multi‐layer formation, and the UV polymerization of the derivatives are reported. magnified image

Preparation of Oriented Large Domains of Diacetylene Monolayer at the Air-Water Interface

Large domains in a diacetylene derivative (10,12-pentacosadiynoic acid) monomer monolayer at the air-water interface were obtained by spreading a solution of relatively high concentration. Uniformly oriented large domains of over 20 mm×5 mm were prepared when the area of water surface was slowly increased by moving a barrier after the highly concentrated solution was spread on a small bounded water surface.

Self-Assembled Monolayers containing Polydiacetylenes

The formation of self-assembled dialkyl disulfide-functionalized monolayers containing diacetylenes is reported for the first time. The diacetylene derivative used was [S(CH 2 ) 2 COO(CH 2 ) 9 ≡C≡CC≡C(CH 2 ) 13 CH 3 ] 2 and was seen to form well-ordered monolayers when adsorbed on gold from THF. The monomer was readily converted to the polymeric form by a short exposure to UV radiation. A «blue» polymer was formed which was stable against further irradiation; that is, it did not become «red». During the polymerization the alkyl side chains displayed some reorganization

Alignment of Surface-Stabilized Ferroelectric Liquid Crystal by the Self-Assembled Monolayers of Amphiphilic Diacetylene Derivatives

Surface-stabilized ferroelectric liquid crystal was aligned by the self-assembled monolayers (SAMs) of amphiphilic diacetylene derivatives formed on an indium tin oxide/glass substrate to maintain bistability when ferro-electric liquid crystal with high spontaneous polarization was used. The SAMs were disposed uniaxially either after rubbing them or passing them through a meniscus at a three-phase contact between a substrate, air, and n-hexane before exposing them to ultra-violet (UV) light. Infrared transmission spectra, contact angles against water and time of flight secondary ion mass spectra have revealed that the modified surface was a sparse monolayer of the diacetylenes, and that they were polymerized by UV light.

FTIR Studies of Trimethylene Linked Bis-Diacetylene Derivatives

Abstract FTIR spectra of a series of bis-diacetylenes were studied. An absorption at about 2255 cm−1 due to stretching vibrations of the diacetylene system (observed in all cases as a relatively intensive peak) has been found to be very characteristic for these diacetylene derivatives, as well as a strong coupling of the CH2 wagging vibration modes resulting in splitting of the absorption peaks at 1300–1360 cm−1.

Diacetylene and polydiacetylene derivatives of 2-methyl-4-nitroaniline for second-harmonic generation

A novel diacetylene derivative of 2-Methyl-4-NitroAniline (MNA), a well-known material for Second-Harmonic Generation (SHG), is synthesized. This monomer DiAcetylene MethylNitroAniline, (DAMNA) is characterized by means of the Kurtz technique at 1064 nm and is found to have an SHG powder efficiency 62.5 % that of MNA itself. Thin crystalline films of DAMNA are grown onto quartz, Teflon, and Kapton substrates by means of vapor deposition in vacuum. These films are then polymerized in the solid state by exposure to long-wavelength UV radiation to give crystalline polydiacetylene thin films (PDAMNA). The films are next characterized for SHG, using an unpolymerized DAMNA film as a reference. Interestingly, films grown onto Teflon exhibit greater orientation and significantly greater SHG than those grown onto quartz and Kapton. This result is promising in that it demonstrates the potential of PDAMNA as both a crystalline and polymeric material for SHG applications, in which highly oriented thin films are desired. Computational modeling (usingAM1) is also carried out on DAMNA and is compared to the experimental results.

Crystal Structure and Solid State Reactivity of Unsymmetrically Aryl-Substituted Diacetylene

Abstract Novel unsymmetrically aryl-substituted diacetylene derivative (1), 4′-(5″-hydroxy-l″,3″-pentadiyny1)benzylidene-p-anisidine, was prepared. Reactivity of polymerization of 1 in the solid state was discussed based on its crystal structure revealed by an X-ray diffraction method.

ChemInform Abstract: Standard Heat of Formation of Some Diacetylene Derivatives

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Absorption, luminescence, resonance Raman, and resonance coherent anti-Stokes Raman spectroscopy on unsymmetrically substituted diacetylene single crystals with color zones

We have analyzed the color zones in single crystals of the diacetylene derivative 6-(p-toluenesulfonyloxy)-2,4-hexadiynyl-p-fluorobenzenesulfonate by means of various optical spectroscopical methods in order to derive a plausible model for the origin of this type of chromism. By applying absorption, luminescence, resonance Raman, and coherent anti-Stokes Raman spectroscopy we obtained sufficient information for an understanding of the nature of the color zones. With the help of a nearly free-electron model calculation and a theoretical model for side group torsions, we found that a disturbance of the π-electron conjugation by a defect hindrance on side groups is the proper reason for the observed chromism. Growth defects in {111} crystal-growth sectors with a Burgers vector in the [010] direction cause the shape of the color zones. We found, particularly, that resonance coherent anti-Stokes Raman spectroscopy proves to be a valuable tool for the investigation of electronic and structural properties of the diacetylene crystals.

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)M. S. Paley, D. O. Frazier, H. Abeledeyem, S. P. McManus, and S. E. ZutautCite this: J. Am. Chem. Soc. 1992, 114, 9, 3247–3251Publication Date (Print):April 1, 1992Publication History Published online1 May 2002Published inissue 1 April 1992https://doi.org/10.1021/ja00035a013RIGHTS & PERMISSIONSArticle Views498Altmetric-Citations26LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (695 KB) Get e-Alerts Get e-Alerts

Second- and Third-Harmonic Generation by Z-Type Langmuir-Blodgett Multilayer Films

Abstract Z-type Langmuir-Blodgett films are prepared from an amphiphilic diacetylene derivative which has been polymerized. The high structural fidelity of these films is verified by optical second and third harmonic generation.

Thermal solid state polymerization of deuterated 2,4‐hexadiynylene di‐p‐toluenesulfonate: The topotactic reaction of topospecifically modified diacetylene derivatives

AbstractThe thermal solid state polymerization was analysed for topospecifically deuterated derivatives of 2,4‐hexadiynylene di‐p‐toluenesulfonate (PTS). Deuteration of the methylene groups close to the diacetylene‐monomer triple bonds influences drastically the length of the induction period and the reaction‐rate constants in the autocatalytic period. These peculiarities were investigated by the combination of dielectric permittivity measurements with differential scanning calorimetry and gravimetrical analyses of the solid state polymerization.

ChemInform Abstract: Synthesis and Characterization of Radical‐Substituted Diacetylene Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis and Characterization of Radical‐Substituted Diacetylene Derivatives

Synthesis and Characterization of Radical‐Substituted Diacetylene Derivatives

The Asymmetrical Diacetylene Derivatives FBS/TFMBS and DNP/MNP: Synthesis and Solid State Properties

AbstractThe synthesis of two new asymmetrical diacetylene (DA) derivatives is described: 1‐(4‐fluorobenzenesulfonyloxy)‐6‐(4‐trifluoromethylbenzenesulfonyloxy)‐2,4‐hexadiyne (FBS/TFMBS) and 1‐(2,4‐dinitrophenoxy)‐6‐(4‐methyl‐2‐nitrophenoxy)‐2,4‐hexadiyne (DNP/MNP). Results are presented on crystal growth, crystal structure analysis and dielectric properties. Both DAs polymerize thermally in the solid state and have polar (“ferroelectric”) individual chains. The different chains in the unit cell are arranged centrosymmetrically in FBS/TFMBS, but non‐centrosymmetrically in DNP/MNP.