Following Sharpless' visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol-ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol-ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.

Thiol–Ene Click Chemistry

The term photonic crystals appears because of the analogy between electron waves in crystals and the light waves in artificial periodic dielectric structures. During the recent years the investigation of one-, two-and three-dimensional periodic structures has attracted a widespread attention of the world optics community because of great potentiality of such structures in advanced applied optical fields. The interest in periodic structures has been stimulated by the fast development of semiconductor technology that now allows the fabrication of artificial structures, whose period is comparable with the wavelength of light in the visible and infrared ranges.

http://ieeexplore.ieee.org/iel5/6354/16969/00781867.pdf

Photonic crystals

Artificially engineered metamaterials are now demonstrating unprecedented electromagnetic properties that cannot be obtained with naturally occurring materials. In particular, they provide a route to creating materials that possess a negative refractive index and offer exciting new prospects for manipulating light. This review describes the recent progress made in creating nanostructured metamaterials with a negative index at optical wavelengths, and discusses some of the devices that could result from these new materials.

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Optical negative-index metamaterials

4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

Near-infrared metamaterials that possess a reconfigurable index of refraction from negative through zero to positive values are presented. Reconfigurability is achieved by cladding thin layers of liquid crystal both as a superstrate and a substrate on an established negative-index metamaterial, and adjusting the permittivity of the liquid crystal. Numerical results show that the index of refraction for the proposed structure can be changed over the range from -1 to +1.8 by tuning the liquid crystal permittivity from 2 to 6 at a wavelength of 1.4 μm.

/pdf/liquid-crystal-clad-near-infrared-metamaterials-with-tunable-2jvvu3o9rs.pdf

Liquid crystal clad near-infrared metamaterials with tunable negative-zero-positive refractive indices

An analysis of aligned nematic liquid crystal cells containing core-shell nanospheres shows that it is possible to devise a new type of metamaterial whose index of refraction is tunable from negative, through zero, to positive values. The design parameters for the constituents can be scaled for application in the optical as well as very long wavelength (e.g., terahertz and microwave) regions.

Nanosphere dispersed liquid crystals for tunable negative-zero-positive index of refraction in the optical and terahertz regimes

Transient and persistent holographic gratings have been observed in dye- and fullerene C60-doped nematic liquid-crystal films. The nature and time evolution of the underlying mechanisms, such as space-charge field production, flows, and dielectric- and conductivity-induced torques, and the resultant director axis reorientation and refractive-index gratings are examined.

Holographic grating formation in dye- and fullerene C(60)-doped nematic liquid-crystal film.

We utilize the properties of aligned nematic liquid crystal (LC) cells in the design of: (i) a new type of metamaterial whose index of refraction is tunable from negative, through zero, to positive values and (ii) micron-scale metallodielectric and all-dielectric tunable frequency selective surfaces (FSSs). The metamaterial is constructed by randomly doping a liquid crystal substrate with coated dielectric (non-magnetic) spheres and can be utilized over a large spectral range. FSSs with a liquid crystal superstrate are synthesized using conventional and genetic algorithm methods to exhibit broadband tunable filter characteristics at mid-infrared (mid-IR) wavelengths. These LC tunable FSS structures can be used to develop a new class of infrared/optical switches for terahertz applications.

Tunable Frequency Selective Surfaces and Negative-Zero-Positive Index Metamaterials Based on Liquid Crystals

We demonstrate a thermally tunable optical metamaterial with negative permeability working in the visible range. By covering coupled metallic nanostrips with aligned nematic liquid crystals (NLCs), the magnetic response wavelength of the metamaterial is effectively tuned through control of the ambient temperature, changing the refractive index of LC via phase transitions. By increasing the ambient temperature from 20 degree to 50 degree, the magnetic response wavelength shifts from 650nm to 632nm. Numerical simulations confirm our tests and match the experimental observations well.

Iam-Choon Khoo

Papers

Liquid crystal clad near-infrared metamaterials with tunable negative-zero-positive refractive indices

Nanosphere dispersed liquid crystals for tunable negative-zero-positive index of refraction in the optical and terahertz regimes

Holographic grating formation in dye- and fullerene C(60)-doped nematic liquid-crystal film.

Tunable Frequency Selective Surfaces and Negative-Zero-Positive Index Metamaterials Based on Liquid Crystals

Tunable magnetic response of metamaterials