Polymers and nonlinear optics

Aromatic, rigid-rod polymers play an important role in a number of diverse technologies, including high-performance engineering materials, conducting polymers, and nonlinear optical materials. 

Carboranes - polyhedral boranes containing carbon in the framework - have been known for over 35 years, and their intrinsic stability, versatility, structural variety, and electronic properties have been put to use in a number of diverse areas, [1] for example in the synthesis of extraordinarily heat-stable polymers, in BNCT (boron neutron capture therapy), as ligands in metallacarborane catalysts, as com-plexing agents for extraction of metal ions, as precursors to ceramics, conducting polymers, and nonlinear optical materials, as anticancer... 

Aromatic rigid-rod polymers play an important role in a number of diverse technologies including high-performance engineering materials, conducting polymers, and nonlinear optical materials. The aoss-coupling reaction of aryldiboronic acids and dihaloarenes for the synthesis of poly(p-phenylenes) was first reported by Rehahn et al. The method has been extensively applied to water-soluble poly(p-phenylene), planar poly(p-phenylenes) fixed with the ketoimine bonds, poly(phenylenes) fused with polycyclic aromatics,and nonlinear optical materials (Scheme 14). 

Liquid crystal polymers are also used in electrooptic displays. Side-chain polymers are quite suitable for this purpose, but usually involve much larger elastic and viscous constants, which slow the response of the device (33). The chiral smectic C phase is perhaps best suited for a polymer field effect device. The abiHty to attach dichroic or fluorescent dyes as a proportion of the side groups opens the door to appHcations not easily achieved with low molecular weight Hquid crystals. Polymers with smectic phases have also been used to create laser writable devices (30). The laser can address areas a few micrometers wide, changing a clear state to a strong scattering state or vice versa. Future uses of Hquid crystal polymers may include data storage devices. Polymers with nonlinear optical properties may also become important for device appHcations. 

J. L. Bredas and R. Silby, Conjugated Polymers The Novel Science and Technology of Highly Conducting and Nonlinear Optically Active Materials, Kluwer Academic, Boston, 1991. 

Secondly, we describe the site-selective introduction of a functional molecule, tetrakis-5,10,15,20-(4-carboxyphenyl)porphyrin (TCPP), into the microphase separation structure of a diblock copolymer film of PS-fo-P4VP. Since porphyrin derivatives show various functionalities such as sensitization, redox activity, and nonlinear optical effect, a polymer nanodot array containing a porphyrin at a high concentration would be applicable to a light-harvesing and charge transporting nanochannel. 

For preparation of dipolar polymers with dielectric properties and nonlinear optical applications, a piperidino-substituted a-cyanocinnamic acid was polycondensed with CDI.[551,tl54]... 

Chiang, W. Thompson, M. E. Van Engen, D. Synthesis and Nonlinear Optical Properties of Inorganic Co-ordination Polymers. In Organic Materials for Nonlinear Optics II Hann, R. A., Bloor, D., Eds. Royal Society of Chemistry London, 1991 pp 210-216. 

The linear and nonlinear optical properties of one-dimensional conjugated polymers contain a wealth of information closely related to the structure and dynamics of the ir-electron distribution and to their interaction with the lattice distorsions. The existing values of the nonlinear susceptibilities indicate that these materials are strong candidates for nonlinear optical devices in different applications. However their time response may be limited by the diffusion time of intrinsic conjugation defects and the electron-phonon coupling. Since these defects arise from competition of resonant chemical structures the possible remedy is to control this competition without affecting the delocalization. The understanding of the polymerisation process is consequently essential. 

This paper will review the linear and nonlinear optical properties of polydiacetylenes with an emphasis on our work with the nBCMU polymers. The following section will discuss material... 

We first discuss the materials research which includes monomer synthesis, growth of monomer crystalline structures and polymerization in the solid state, yielding the requisite polymer structures. Next, the nonlinear optical experimental research is discussed which includes a novel experimental technique to measure x (w). Linear and nonlinear optical data obtained for the polydiacetylene films is subsequently presented. Detailed theoretical analysis relating the data to x (< >) and subsequently to its molecular basis will be discussed in a later publication. 

The Suzuki coupling has been utilized to craft (Toctasubstituted tetramesitylporphyrins using various arylboronic acids [62], and Schluter has adopted this reaction to prepare phenyl-pyrrole mixed polymers 75 [63]. The BOC group is easily removed by heating [64] and polymers with molecular weights of up to 23,000 were synthesized. These polymers are potentiaEy interesting for their electrical and nonlinear optical properties [65]. 

Oligomerization and polymerization of terminal alkynes may provide materials with interesting conductivity and (nonlinear) optical properties. Phenylacetylene and 4-ethynyltoluene were polymerized in water/methanol homogeneous solutions and in water/chloroform biphasic systems using [RhCl(CO)(TPPTS)2] and [IrCl(CO)(TPPTS)2] as catalysts [37], The complexes themselves were rather inefficient, however, the catalytic activity could be substantially increased by addition of MesNO in order to remove the carbonyl ligand from the coordination sphere of the metals. The polymers obtained had an average molecular mass of = 3150-16300. The rhodium catalyst worked at room temperature providing polymers with cis-transoid structure, while [IrCl(CO)(TPPTS)2] required 80 °C and led to the formation of frani -polymers. 

Ramasesha, S., Pati, S.K., Krishnamurthy, H.R., Shuai, Z., Bredas, J.L. Low-lying electronic excitations and nonlinear optic properties of polymers via symmetrized density matrix renormalization group method. Synth. Met. 1997, 85(1-3), 1019. 

The driving force in polymer synthesis is the search for new polymers with improved properties to replace other materials of construction. Polymers are lightweight and can be processed easily and economically into a wide range of shapes and forms. The major synthetic efforts at present are aimed at polymers with high temperature, liquid crystal, conducting, and nonlinear optical properties [Maier et al., 2001 Sillion, 1999]. There is an interrelationship between these efforts as will become apparent. 

Lee and co-workers reported an interesting example of a conjugated polymer obtained by polymerizing 5-phenyl-2-(propynylamino)-4(57/)-oxazolone in the presence of palladium or platinum chlorides. The authors predict this unique material may have applications for polymer electrolytes, semiconductors, and nonlinear optical (NLO) materials. 

A number of liquid crystalline polyphosphazenes with mesogenic side groups have been prepared (48—50). Polymers with nonlinear optical activity have also been reported (51). Polyphosphazene membranes have been examined for gas, liquid, and metal ion separation, and for filtration (52—54). There is interest in phosphazene—organic copolymers, blends, and interpenetrating polymer networks (IPNs) (55—61) to take advantage of some of the special characteristics of phosphazenes such as flame retardance and low temperature flexibility. A large number of organic polymers with cydophosphazene substituents have been made (62). 

As a conducting polymer, polyaniline has many electronics-related applications, such as rechargeable batteries (Tsutsumi et al. 1995), multilayer heterostructure light-emitting diode devices (Onoda Yoshino 1995), biosensors (Bartlett Whitaker 1987), elec-trochromic windows (Nguyen Dao 1989), and nonlinear optical materials (Papacostadi-nou Theophilou 1991). Polyaniline may be prepared from aniline by both electrochemi-... 

Alkyloxythiophene derivatives can be connected to an azobenzene moiety and the polymer showed nonlinear optical properties (03SM(138) 409 04MI2117 05MI2360). 

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