Postfunctionalization of poly(propargyl methacrylate) using copper catalyzed 1,3‐dipolar Huisgen cycloaddition: An easy route to electro‐optic materials
Annabelle ScarpaciClément CabanetosErrol BlartVéronique MontembaultLaurent FontaineVincent RodriguezFabrice Odobel
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Abstract A one‐pot synthetic route based on copper‐catalyzed Huisgen reaction has been developed to functionalize a methacrylate propargylic polymer with azido‐substituted moieties. This procedure was used for the preparation of electro‐optic materials containing well‐known Disperse Red One (DR1) chromophores along with bulky adamantyl moieties (Adam). The postfunctionalization of the propargylic polymer was successfully achieved using different molar ratios of DR1/Adam. These novel polymers exhibit high glass transition temperature owing to the rigid structure of adamantyl units. Moreover, the second harmonic generation measurements demonstrated the effectiveness of adamantyl groups to act as insulating shield limiting thus the electrostatic interactions between chromophores. Indeed, higher optimal chromophore concentration (50 mol %) than in conventional DR1‐containing polymers (30 mol %) allowed us to increase the d 33 coefficient up to 92 pm/V. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5652–5660, 2009Keywords:
Chromophore
Propargyl
We have successfully synthesized several new substituted thiophene-based electro-optic chromophores. All of these chromophores have structures similar to FTC but they incorporated our newly designed tricyanovinyldihydrofuran acceptors. Since these acceptors possess an anisotropic structure, all of the chromophores are very soluble in a wide range of organic solvents. Thermal study of these chromophores by TGA shows all of them are very stable in air. UV spectra indicate the chromophores have a large solvatochromic effect, implying very large molecular nonlinearities.
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Solvatochromism
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The enantioselective N-heterocyclic carbene-catalysed formal 2+2- and 2+2+2- cycloadditions of ketenes with isothiocyanates can be investigated. At room temperature, the reaction of N-arylthiocyanates favours the 2+2-cycloaddition. However, at −40°C, N-benzoylisothiocyanates undergo the 2+2+2-cycloaddition. This chapter discusses cycloaddition-type addition reactions. Specifically, it covers three types of cycloadditions: 2+2-cycloaddition, 2+3-cycloaddition and 2+4-cycloaddition. Miscellaneous cycloaddition reactions are separately described at the end of the chapter.
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Research to determine the mechanisms which tie chromophore reorientation to polymer relaxation is crucial to the development of thermally stable NLO polymers. 1 Most of the work to date has been performed above or near the glass transition temperature where the decay of the NLO properties of the material is tied to the glass transition and the α -motion of the polymer backbone. Devices which rely upon permanently poled polymer films for their NLO characteristics are not designed to operate near or above the glass transition because their nonlinear properties would quickly dissipate. A study of the coupling between polymer motion and chromophore reorientation below the glass transition temperature is necessary to gain insight into the reorientional dynamics of the chromophores at common device temperatures. Using the results of elevated temperature studies to predict the behavior of the NLO properties below T g may not be accurate if the mechanisms responsible for chromophore reorientation are not the same in both regimes.
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Translational motion
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Abstract Metal-catalyzed [2+2+2] cycloaddition is a powerful tool that allows rapid construction of functionalized 6-membered carbo- and heterocycles in a single step through an atom-economical process with high functional group tolerance. The reaction is usually regio- and chemoselective although selectivity issues can still be challenging for intermolecular reactions involving the cross-[2+2+2] cycloaddition of two or three different alkynes and various strategies have been developed to attain high selectivities. Furthermore, enantioselective [2+2+2] cycloaddition is an efficient means to create central, axial, and planar chirality and a variety of chiral organometallic complexes can be used for asymmetric transition-metal-catalyzed inter- and intramolecular reactions. This review summarizes the recent advances in the field of [2+2+2] cycloaddition. 1 Introduction 2 Formation of Carbocycles 2.1 Intermolecular Reactions 2.1.1 Cyclotrimerization of Alkynes 2.1.2 [2+2+2] Cycloaddition of Two Different Alkynes 2.1.3 [2+2+2] Cycloaddition of Alkynes/Alkenes with Alkenes/Enamides 2.2 Partially Intramolecular [2+2+2] Cycloaddition Reactions 2.2.1 Rhodium-Catalyzed [2+2+2] Cycloaddition 2.2.2 Molybdenum-Catalyzed [2+2+2] Cycloaddition 2.2.3 Cobalt-Catalyzed [2+2+2] Cycloaddition 2.2.4 Ruthenium-Catalyzed [2+2+2] Cycloaddition 2.2.5 Other Metal-Catalyzed [2+2+2] Cycloaddition 2.3 Totally Intramolecular [2+2+2] Cycloaddition Reactions 3 Formation of Heterocycles 3.1 Cycloaddition of Alkynes with Nitriles 3.2 Cycloaddition of 1,6-Diynes with Cyanamides 3.3 Cycloaddition of 1,6-Diynes with Selenocyanates 3.4 Cycloaddition of Imines with Allenes or Alkenes 3.5 Cycloaddition of (Thio)Cyanates and Isocyanates 3.6 Cycloaddition of 1,3,5-Triazines with Allenes 3.7 Cycloaddition of Aldehydes with Enynes or Allenes/Alkenes 3.8 Totally Intramolecular [2+2+2] Cycloaddition Reactions 4 Conclusion
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Hyperpolarizability
Thermal Stability
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Abstract Acetylene and ethylene are the smallest molecules that contain an unsaturated carbon–carbon bond and can be efficiently utilized in a large variety of cycloaddition reactions. In this review, we summarize the application of these C2 molecular units in cycloaddition chemistry and highlight their amazing synthetic opportunities. 1 Introduction 2 Fundamental Features and Differences of Cycloaddition Reactions Involving Acetylene and Ethylene 3 (2+1) Cycloaddition 4 [2+2] Cycloaddition 5 (3+2) Cycloaddition 6 [4+2] Cycloaddition 7 (2+2+1) Cycloaddition 8 [2+2+2] Cycloaddition 9 The Use of Acetylene and Ethylene Cycloaddition for Deuterium and 13C Labeling 10 Conclusions
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Phenoxazine
Thermal Stability
Acceptor
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When analyzing the emission of a large number of individual chromophores embedded in a matrix, the spread of the observed parameters is a characteristic property for the particular chromophore−matrix system. To quantitatively assess the influence of the matrix on the single molecule emission parameters, it is imperative to have a system with a well-defined chromophore nanoenvironment and the possibility to alter these surroundings in a precisely controlled way. Such a system is available in the form of the visible fluorescent proteins, where the chromophore nanoenvironment is defined by the specific protein sequence. We analyze the influence of the chromophore embedding within this defined protein environment on the distribution of the emission maximum wavelength for a number of variants of the fluorescent protein DsRed, and show that this parameter is characteristic of the chromophore−protein matrix combination and largely independent of experimental conditions. We observe that the chemical changes in the vicinity of the chromophore of different variants do not account for the different distributions of emission maximum positions but that the flexibility of the chromophore surrounding has a dominant role in determining the distribution. We find, surprisingly, that the more rigid the chromophore surrounding, the broader the distribution of observed maximum positions. We hypothesize that, after a thermally induced reorientation in the chromophore surrounding, a more flexible system can easily return to its energetic minimum position by fast reorientation, while in more rigid systems the return to the energetic minimum occurs in a stepwise fashion, leading to the broader distribution observed.
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Oligomer
Matrix (chemical analysis)
Fluorescent protein
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This chapter contains sections titled: Introduction and Extent of This Chapter Propargyl Esters Propargyl Ethers Propargyl Alcohols Propargyl Amines Propargyl Carbonates, Amides, and Carbamates Other Propargyl Substitution Patterns Conclusion References
Propargyl
Propargyl alcohol
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