Polymeric nonlinear optical materials

Design and Characterization of Molecular and Polymeric Nonlinear Optical Materials ... 

Synthetic Approaches to Polymeric Nonlinear Optical Materials Based on Ferrocene Systems... 

Champagne, B., Kirtman, B. Theoretical approach to the design of organic molecular and polymeric nonlinear optical materials. In Handbook of Advanced Electronic and Photonic Materials and Devices, vol. 9. Academic, San Diego (2001)... 

A new type of nano-layered polymeric nonlinear optical material for optical limiting applications has been fabricated. It comprises alternating polymer layers with thousands of layers and a layer thickness down to 30 nm or less. By introducing appropriate dyes into alternate polymer layers, a material with a modulation in the real and/or imaginary part of the nonlinear refractive index in the direction normal to the surface is possible. 

Historically, polymeric nonlinear optical materials have ranged from chromophores physically incorporated (i.e., dissolved) in polymer hosts to form composite materials, to chromophores attached by a single covalent bond to a polymer backbone, to chromophores attached at both ends to a polymer network. The physical incorporation of chromophores into polymer hosts to form composites typically... 

Hubbard, M. A., Marks, T. J., Lin, W., and Wong, G. K., Poled polymeric nonlinear optical materials. Enhanced second harmonic generation temporal. stability of epoxy-based matrixes containing a difunctional chromophoric comonomer, Chem. Mater., 4, 965-968 (1992). 

Meredith, G. R., Design and characterization of molecular and polymeric nonlinear optical materials successes and pitfalls, in Nonlinear Optical Properties of Organic and Polymeric Materials (ACS Symp. Sen, 233), Williams, D. J., Ed., American Chemical Society, Washington, D.C., 1983, 27. 

The cadmium chalcogenide semiconductors (qv) have found numerous appHcations ranging from rectifiers to photoconductive detectors in smoke alarms. Many Cd compounds, eg, sulfide, tungstate, selenide, teUuride, and oxide, are used as phosphors in luminescent screens and scintiUation counters. Glass colored with cadmium sulfoselenides is used as a color filter in spectroscopy and has recently attracted attention as a third-order, nonlinear optical switching material (see Nonlinear optical materials). DiaLkylcadmium compounds are polymerization catalysts for production of poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVA), and poly(methyl methacrylate) (PMMA). Mixed with TiCl, they catalyze the polymerization of ethylene and propylene. 

While the amount of electricity that can be conducted by polymer films and wires is limited, on a weight basis the conductivity is comparable with that of copper. These polymeric conductors are lighter, some are more flexible, and they can be laid down in wires that approach being one-atom thick. They are being used as cathodes and solid electrolytes in batteries, and potential uses include in fuel cells, smart windows, nonlinear optical materials, LEDs, conductive coatings, sensors, electronic displays, and in electromagnetic shielding. 

Finally, the combination of dendrimers and organometallic entities as fundamental building blocks affords an opportunity to construct an infinite variety of organometallic starburst polymeric superstructures of nanoscopic, microscopic, and even macroscopic dimensions. These may represent a promising class of organometallic materials due to their specific properties, and potential applications as magnetic ceramic precursors, nonlinear optical materials, and liquid crystal devices in nanoscale technology. 

Polysilane high polymers possessing fully saturated all-silicon backbone have attracted remarkable attention recently because of their unique optoelectronic properties and their importance in possible applications as photoresists, photoconductors, polymerization initiators, nonlinear optical materials etc. A number of review articles have been published on this topic4-9. The studies in this field have stimulated both experimental and theoretical chemists to elaborate on understanding the excited state nature of polysilanes and oligosilanes and of their mechanistic photochemistry. 

Understandably, there is an enormous richness in the photophysical and photochemical behavior of the excited states present in diimine rhenium tricarbonyl complexes. Indeed, this plethora of molecular photophysical characteristics has led to a wide range of interesting and important applications, including their use as catalysts [21-25], sensors [26-33], probes for photo-polymerization [10, 34, 35], optical switches [36 15], light-emitting materials [46-52], nonlinear optical materials [53-56], binding or photocleavage of DNA [57-61], and radiopharmaceuticals [62-66], Under the purview of this article our focus will be to cover photophysical and photochemical properties and hence other aspects, such as synthetic, catalytic, pharmaceutical, etc., will not be discussed. 

Side-chain liquid-crystalline polymers with controlled molecular weights have been obtained by the polymerization of FM-25 with 1-22 (X = Br)/CuBr/ L-3 in the bulk at 100 °C, to examine the thermotropic transition as a function of the MWD.324 Second-order nonlinear optical materials with branched structure were prepared by the copper-catalyzed radical polymerization of FM-26 and FM-27 using hyperbranched poly[4-(chloromethyl)styrene] as a multifunctional initiator.325... 

The self-condensing copper-catalyzed polymerization of macromonomer of poly(tBA) with a reactive C—Br bond (H-6) affords hyperbranched or highly branched poly(tBA).447 Copolymerization of H-1 and TV-cyclohexylmaleimide induced alternating and self-condensing vinyl polymerization.448 The residual C—Cl bond was further employed for the copper-catalyzed radical homopolymerization of styrene to give star polymers with hyperbranched structures. Hyperbranched polymers of H-1 further serve as a complex multifunctionalized macroinitiator for the copper-catalyzed polymerization of a functional monomer with polar chromophores to yield possible second-order nonlinear optical materials.325... 

Organic compounds with delocalized jr-electron systems, e,g., jr-conjugated polymers, are considered to be candidates for third-order nonlinear optical materials. Among them, polydiacetylenes (PDAs) are an important class of conjugated polymers that has attracted investigators from many different fields (7,2). PDAs, which can be obtained as single crystals by topochemical solid-state polymerization (5), have been extensively studied since 1976 (4). PDAs show large third-order nonlinear optical susceptibilities (5) and ultrafast optical... 

Nanostructured Polymeric Nonlinear Photonic Materials for Optical Limiting... 

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