ISSN 0012-5008, Doklady Chemistry, 2012, Vol. 446, Part 1, pp. 183–187. © Pleiades Publishing, Ltd., 2012. Original Russian Text © S.M. Igumnov, V.I. Sokolov, V.K. Men’shikov, O.A. Mel’nik, V.E. Boiko, V.I. Dyachenko, L.N. Nikitin, E.V. Khaidukov, G.Yu. Yurkov, V.M. Buznik, 2012, published in Doklady Akademii Nauk, 2012, Vol. 446, No. 3, pp. 288–293. 183 Nowadays, fluorinated polymeric materials are increasingly used in integrated optics owing to their high functionality and manufacturability [1–4]. As distinct from hydrocarbon polymers, fluorinated poly- mers have lower absorption in all three telecom wave- length ranges near 0.85, 1.3, and 1.55 μm. This is caused by the fact that the stretching vibra- tion overtones of the C–F bonds are shifted toward longer wavelengths as compared with the C–H over- tones responsible for the absorption in the given spec- tral ranges [5]. Yet another specific feature of fluori- nated monomers is the low refractive index (n D ). The copolymerization of fluorinated and non-fluorinated monomers makes it possible to vary the refractive index of the composition in wide ranges, which is important for fabrication of waveguides with a speci- fied numerical aperture. Finally, fluorinated polymers are more thermostable and more resistant to degrada- tion, color change, etc. This is due to the fact that the C–F bond energy is much higher than the C–H bond energy. Monomers for producing integrated optical devices (for example, optical waveguides) should have some specific properties. First, they should have high optical transparency in the working range of the spectrum. Second, monomers should be rather active in the pro- cess of radical photopolymerization since waveguides are fabricated by UV photolithography. This is associ- ated with the fact that the cross-sectional dimensions of waveguides are very small: their height and width range from a few to several tens of microns. Third, monomers with high and low refractive indices intended to be the components of the compositions for the light-guiding core and the waveguide cladding should readily copolymerize with each other. This work is aimed at synthesizing new fluorinated monomers exhibiting the above set of useful properties and at studying the possibility of using them for fabri- cation of polymer waveguides. As is known, perfluoroolefins 1-1, unlike the non- fluorinated analogues, react with KF to form metasta- ble reactive carbanions 1-2. This is attested by a mul- titude of chemical transformations on their basis; in addition, they have been detected by 19 F NMR [6]. The primary addition of the fluoride ion to the double bond of a perfluoroalkene followed by stabilization of the resulting carbanion with the potassium cations occurs smoothly in polar solvents with high solvation ability (Scheme 1). Scheme 1. It has been shown that the perfluoroalkyl carbanion can be sometimes stabilized with an organic carboca- tion rather than an inorganic counterion (K + , Сs + , etc.) [7]. Reactions with intermediate formation of polyfluorocarbanions occupy a prominent place in the chemistry of fluoroolefins [8–10]. Their in situ gener- ation in the reaction mixture in the presence of various electrophilic agents, such as diazo compounds, α- oxides, sultones, isocyanates, sulfenyl chlorides, and alkyl halides, enables the synthesis of new organofluo- rine compounds and monomers for polymer chemis- try [11]. Using the commercially available perfluoroolefin 1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)-2- R f2 R f1 F F C R f2 R f1 F F F 1-1 1-2 + F – K + K + – R f 1 R f 2 R f 1 R f 2 CHEMISTRY Fluorinated Monomers and Polymers with Specific Properties for Integrated Optics and Photonics S. M. Igumnov, V. I. Sokolov, V. K. Men’shikov, O. A. Mel’nik, V. E. Boiko, V. I. Dyachenko, L. N. Nikitin, E. V. Khaidukov, G. Yu. Yurkov, and Academician V. M. Buznik Received March 23, 2012 DOI: 10.1134/S0012500812090066 Nesmeyanov Institute of Organoelement Chemistry, Russian Academy of Sciences, ul. Vavilova 28, Moscow 119991 Russia Institute of Problems of Laser and Information Technologies, Russian Academy of Sciences, ul. Svyatoozerskaya 1, Shatura, Moscow oblast, 140700 Russia Baikov Institute of Metallurgy, Leninskii pr. 49, Moscow, 119991 Russia