This paper reports synthesis, characterization and structural optimization of amino-thienyl-dioxocyano-pyridine (ATOP) chromophores toward a multifunctional amorphous material with unprecedented photorefractive performance. The structural (dynamic NMR, XRD) and electronic (UV/vis, electrooptical absorption, Kerr effect measurements) characterization of the ATOP chromophore revealed a cyanine-type pi-conjugated system with an intense and narrow absorption band (epsilon(max) = 140 000 L mol(-)(1) cm(-)(1)), high polarizability anisotropy (deltaalpha(0) = 55 x 10(-)(40) C V(-)(1) m(2)), and a large dipole moment (13 D). This combination of molecular electronic properties is a prerequisite for strong electrooptical response in photorefractive materials with low glass-transition temperature (T(g)). Other important materials-related properties such as compatibility with the photoconducting poly(N-vinylcarbazole) (PVK) host matrix, low melting point, low T(g), and film-forming capabilities were optimized by variation of four different alkyl substituents attached to the ATOP core. A morphologically stable PVK-based composite containing 40 wt % of ATOP-3 showed an excellent photorefractive response characterized by a refractive index modulation of Deltan approximately 0.007 and a gain coefficient of Gamma approximately 180 cm(-)(1) at a moderate electrical field strength of E = 35 V microm(-)(1). Even larger effects were observed with thin amorphous films consisting of the pure glass-forming dye ATOP-4 (T(g) = 16 degrees C) and 1 wt % of the photosensitizer 2,4,7-trinitro-9-fluorenylidene-malononitrile (TNFM). This material showed complete internal diffraction at a field strength of only E = 10 V microm(-)(1) and Deltan reached 0.01 at only E = 22 V microm(-)(1) without addition of any specific photoconductor.

Tetraphenoxy-substituted diazadibenzoperylenes 5a,b were synthesized from tetrachloroperylene tetracarboxylic acid bisanhydride 1 through imidization with benzylamine, nucleophilic displacement of the four chlorine atoms by phenolates, carbonyl group reduction by LiAlH(4)/AlCl(3), and subsequent Pd/C-promoted debenzylation-dehydrogenation. The structural properties of these extended diazaarenes are discussed on the basis of a X-ray crystal structure of the N,N'-dibutylated diazadibenzoperylenium dication 6, which revealed a 25 degrees twist of the central six-membered ring leading to an atropisomeric pi-conjugated backbone. The chromophoric systems of 5 and 6 were characterized by optical absorption and fluorescence spectroscopy, which revealed an intense fluorescence with a quantum yield of 75% for 5 and 50% for 6. Cyclic voltammetry showed reversible oxidation and reduction waves for 6, whereas the oxidation of 5 afforded the irreversible deposition of a conductive film on the electrode surface. Finally, the potential use of ligands 5 in supramolecular chemistry has been evaluated by complexation experiments with carboxylic acids and zinc tetraphenylporphyrin (ZnTPP).

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