Electrooptical (EO) materials are able to change their refractive index under the influence of an externally applied electric field, an effect that is of great technological importance as a means to control the phase of laser light. [1] In recent years, a variety of cheap and easily processable organic nonlinear optical (NLO) materials [2] were designed for this purpose. Poled polymers for high-frequency modulation of optical signals were developed, and photorefractive (PR) polymers [3] emerged as promising materials for widespread holographic optical applications. In both types of material, the EO response is provided by chromophores that are usually incorporated into the material as guests or as side-groups in functionalized polymers. In this communication, we analyze the microscopic mechanism leading to the refractive index modulation and define appropriate molecular figures-of-merit (FOMs) for EO chromophores, F 0 Pockels and F 0 Kerr . In order to investigate optimization strategies for both FOMs, we synthesized a series of dyes based on quinonoid carbocyclic and heterocyclic acceptor units, which exhibit significantly higher acceptor strength and better thermal stability than common open-chain acceptor groups.All chromophores investigated in this study are displayed in Figure 1. The synthetic procedures for the new EO dyes 4±11 are shown in Schemes 1 and 2. Accordingly, EO dyes 4 and 10 were prepared by Knoevenagel condensations of p-N,N-dimethylamino cinnamaldehyde (13a) with benzylidene malononitrile 15 [4] and 1-naphthylmalononitrile (16) [5] in acetic acid anhydride in yields of 72 and 43 %, respectively (Scheme 1). Similarly, dye 3 (DCM, a commercial laser dye) was obtained according to the literature from 14. [6] For dye 11, the polyenic chain of 13b was extended via a Wittig oxopropenylation [7] using the protected formylmethylenetriphenylphosphorane 17 to give pentadienal 18 in 60 % yield. The following condensation of 18 with 16 gave 11 in 10 % yield. The EO dyes 5±9, bearing the new powerful thiazolidenemalononitrile acceptor unit, were synthesized according to Scheme 2. Reaction of stoichiometric amounts of a-thiocyanatoketones 19a and b with malononitrile afforded 2-dicyanomethylthiazoles 20a and b in almost quantitative yields. [8] Because of an equilibrium between various tautomeric forms, these heterocycles may react easily in condensation reactions with aldehydes 13a and b, 21, and 22 to give dyes 5, 6, and 9a and b in yields of 60±80 %. The corresponding aldehydes 21 and 22 were obtained from N,N-dibutylaniline and N-alkylated 3,3-dimethyl-2-methyleneindoline by Vilsmeier formylations. For the synthesis of EO dyes 7 and 8 the reaction conditions had to be changed because of the high basicity of the methylene bases of 23 and 24. In a one-pot sequence in acetic acid anhydride, 3ethyl-2-methylbenzoxazolium iodide (23) and 1-hexyl-4methylpyridinium bromide (24) were first converted to the anils by N,N-diphenylformamidine (DPFA). They were then in-situ N-acetylated at 150 C, [9] before being ...