Two new extended chromophoric systems, in which a 4-aminoazobenzene moiety is linked to a cyclo-bridged hexatriene electron withdrawing group, have been synthesized, and show large optical nonlinearities and unexpected blue-shifted absorption in comparison with shorter chain analogues.

A new intercalation compound Mn0.84PS3(phen)0.64 (phen5 1,10-phenanthroline) was synthesized in one step by direct reaction of host MnPS3 with 1,10-phenanthroline, which was characterized by elemental analysis, X-ray powder di4raction, and infrared spectroscopy. As a result of intercalation, the lattice spacing of the intercalate expanded by 8.63 A with respect to the pristine MnPS3. For comparison, another new intercalation compound Mn0.88PS3[Mn(phen)4]0.12(H2O) was also prepared in two steps by means of ion exchange. The studies of magnetic properties with SQUID-magnetometer indicated that the two intercalates, Mn0.84PS3(phen)0.64 and Mn0.88PS3[Mn(phen)4]0.12 (H2O), exhibit bulk spontaneous magnetization below 36 and 33 K, respectively.

The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4-(4-hydroxyaryl)phthalazin-1(2H)-ones (2a-2d), were conveniently and efficiently synt esized from phenols and phthalic anhydride in two steps via 2-(4-hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel-Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a-2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (SNAr) polycondensation between the compounds perfluorobiphenyl and 4-(4 -hydroxyaryl)phthalazin-1(2H)-ones (2a-2d). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl3, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc.) at room temperature. Their weight-average molecular weights and the polydispersities ranged from (7.96-18.25)×103 to 1.31-2.71, respectively. Their glass-transition temperatures varied from 213 to 263℃. They were all stable up to 390℃ both in air and in argon. The 5% weight-loss temperatures of these polymers in air and argon ranged from 393-487 to 437-509℃, respectively. Wide-angle X-ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone.

This paper summarizes our research on the synthesis and properties of several kinds of functionalized polysilanes (FPSs) containing nonlinear optic (NLO) chromophores in the side chain. They have been synthesized successfully through utilizing different synthetic strategies: chloromethylation of poly(methylphenylsilanes) and the following etherification with the hydroxycontaining NLO chromophore in water /chloroform two-phase system with Brij35 as a phase-transfer catalyst; hydrosilylation of polyhydrosilanes with the NLO chromophore containing the terminal double bond; etherification of chlorine-containing polysilanes with the hydroxy-containing NLO chromophore; and postunctionalization of phenyl group-containing polysilanes through azo coupling with p-nitrobenzenediazonium fluoroborate or tricyanovinylation with the oxidant tetracyanoethylene. FPSs were characterized with FT-IR, UV/vis spectra, differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and elemental analysis. The second-order optical nonlinear properties of the polysilanes were determined by in situ second harmonic generation (SHG) experiments.

)mc, with a=7.7281(14) Å, b=7.7281(14) Å, c=6.742(2) Å,α=90°, β=90°, γ=120°, Z=2. It was obtained by a new preparation procedure different from that reported in the literature that gave a centrosymmetric structure. The structure contains Cd-Br octahedrons, which are connected in a plane-sharing way to form edimensional long chains. Each octahedron is slightly distorted, as the three Cd-Br bond lengths are 2.774 Å, while the other three Cd-Br bond lengths are 2.804 Å. The distortion directions of all of the octahedrons are almost parallel and give rise to the accumulation of the microcosmic nonlinear optical (NLO) coefficient. The Kurtz powder technique shows that CsCdBr3 has a powder second harmonic generation of about 2 times as large as that of potassium dihydrogen phosphate (KDP). It shows excellent ransparency in the visible and infrared regions. The thermal stability is also good. Therefore it may be utilized as a potential nonlinear optical crystal for the IR region.