Nonlinear optical properties polydiacetylenes

The nonlinear optical properties of novel, soluble polydiacetylenes are reviewed and discussed. 

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... 

For the elucidation of the optical and nonlinear optical properties of the polydiacetylene layers, we have employed a wave-... 

Linear and nonlinear optical properties of a class of polydiacetylenes that can be grown as large area and controlled thickness thin films have been investigated. This involved an integrated research effort including monomer synthesis, thin film growth and new measurement techniques. 

Nakanishi H, Katagi H (1998) Microcrystals of polydiacetylene derivatives and their linear and nonlinear optical properties. Supramol Sci 5 289-295... 

Polydiacetylenes are obtained as single crystals by topochemical solid-state polymerization of the monomer single crystal. These compounds have received considerable attention because of their one-dimensionally -conjugated structure. Their unique --electron structures, and therefore superior third-order nonlinear optical properties, have been extensively investigated. 

Huggins KE, Son S, Stupp SI. Two-dimensional suptamolecular assemblies of a polydiacetylene. 1. Synthesis, structure, and third-order nonlinear optical properties. Macromolecules 1997 30 5305-5312. 

Conjugated polymers satisfy these requirements and have thus emerged as the most widely studied materials for their susceptability. Some of the examples of conjugated polymers, that have been studied for their third order NLO properties, are polydiacetylenes, poly-p-phenylenevinylenes and polythiophenes. However, CVD has only been used in the case of poly-p-phenylenevinylenes (PPV) [section 3.4], although values have not been reported. An excellent review of third order nonlinear optical properties of PPV in general, can be found in literature. Recently, McElvain et al. ° reported the values of CVD polyazomethines to be... 

Camacho, M.A., Kar, A.K., Lindsell, W.E.. Murray, C., Preston, P.N., Wherrett, B.S. Synthesis and nonlinear optical properties of functionalized polydiacetylenes and their complexes with transition metals. J. Mater. Chem. 9, 1251-1256 (1999)... 

This reaction, called a four-center photopolymerization, is a typical example of topochemical reactions used to prepare polymer crystals.5 The changes in higher-order structure during the reaction are shown in Table 2.5 . Various polydiacetylene crystals have also been prepared by solid-state photopolymerization of diacetylene monomer crystals, such as 1,6-dicarbazoyl-2,4-hexadiene. These syntheses have attracted considerable interest, since they can lead to organic materials of high conductivity or of nonlinear optical properties. 

The values shown in the table are smaller for polydiacetylene than for polyene and polyyne. This is likely due to the fact that addition of a non-conjugated r-bond makes an almost additive perturbation to the r-system and leads to a reduction of the specific (per atom) linear size. Also, as could be seen from Table 3.11, the largest values of the specific (per atom) nonlinear optical properties among all considered polymers are obtained for polyynes. 

The nonlinear optical properties of polydiacetylenes are subject of an increasing interest in last years (1-4). This is due to the fact that polydiacetylenes are a one-dimensionnal system of higly polarizable conjugated tt elections The polarization depends strongly on electron delocalization length Moreover, the electronic origin of hyperpolarizability implies short response times On the other hand, the wave dispersed measurements of molecular hyperpolarizabilities yield information about forbidden electronic transitions In fact the bulk polarization can be developped in external electric field power series ... 

A number of studiesof the nonlinear optical properties of polydiacetylene multilayers have been undertaken. It is obvious from these investigations that there is a strong possibility.that these materials have applications in integrated optics as wave guide materials. However this will be dependent on the ability to control morphology and structure in these layers, thus indicating the... 

The synthesis of polydiacetylenes with bipyridine metal complexes in their sidechains has been achieved by Lindsell and cowoikers (Scheme 17). Complexes of nickel, copper, ruthenimn, and molybdenum were synthesized and the nonlinear optical properties of the resulting polymers examined. 

Nakanishi, H., Matsuda, H., Takaragi, S., Okada, S., and Kato, M., Novel blue-colored polydiacetylenes for nonlinear optics, in Nonlinear Optical Properties of Materials 1988 Technical Digest Sen, 9), OSA, Washington, D.C., 1988, 182. 

Okada, S., Doi, T., Mito, A., Hayamizu, K., Ticktin, A., Matsuda, H., Kikuchi, N., Masaki, A., Minami, N., Haas, K.-H., and Nakanishi, H., Synthesis and third-order nonlinear optical properties of a polydiacetylene from an octatetrayne derivative with urethane groups. Nonlinear Opt., 8, 121, 1994. 

Kanetake, T., Ishikawa, K., Hasegawa, T., Koda, T., Takeda, K., Hasegawa, M., Kubodera, K., and Kobayashi, H., Nonlinear optical properties of highly oriented polydiacetylene evaporated films, Appl. Phys. Lett., 54, 2287, 1989. 

Thakur, M. Verbeek, B. Chi, G.C. O Brien, K.J., "Some Fundamental Aspects of the Thin Film Organization and Device-Structure Fabrication of Polydiacetylenes", p. 41 in Heeger, A.J. Orenstein, J. Ulrich, D.R. (Eds.), Mat. Res. Soc. Symp. Proc., Vol. 109 Nonlinear Optical Properties of Polymers, Materials Research Society, Pittsburgh, Pennsylvania, USA (1998). 

He, J. A., et al., Electrostatic self-assembly of polydiacetylene nanocrystals nonlinear optical properties and chain orientation. J Phys Chem B, 1999. 103(50) p. 11050-11056. 

CHARRA F. and NUNZI J.M., (1989b), "Strong Field Nonlinear Optical Properties of Polydiacetylenes" in Nonlinear Optical Materials II, J.B. Grun ed., Proc. SPIE, Vol. 1127, 173-181. 

KANETAKE T., ISHIKAWA K., HASEGAWA T., KODA T., TAKEDA K., HASEGAWA M., KUBODERA K. and KOBAYASHI M., (I989), "Nonlinear Optical Properties of Highly Oriented Polydiacetylene Evaporated Films", Appl. Phys. Lett.,... 

Ohnishi, S., Orimoto, Y, Gu, F.L., Aoki, Y Nonlinear optical properties of polydiacetylene with donor-acceptor substitution block. J. Chem. Rhys. 127, 084702 (2007)... 

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