A new series of substituted poly(ferrocenylsilane)(3a-3c) were synthesized through transition-metal catalyzed ring-opening polymerization (ROP) of the corresponding [1]silaferrocenophanes (2a-2c). The structural characterization is presented with 1H-NMR, FT-IR, gel permeation chromatography (GPC), and differential scanning calorimeter (DSC). These polymers were doped with tetracyanoethylene (TCNE). The magnetic property of doped product (4c) was studied by SQUID measurement, and which indicated that this doped product showed paramagnetism with below 110 K.

A new synthetic strategy was developed to prepare polyphosphazenes with second-order nonlinear optical chromophore in which sulfonyl groups are the acceptors. Thus, polyphosphazenes P1 and P2 that contain aniline or indole groups as side chains were obtained from a highly reactive macromolecular intermediate, poly(dichlorophosphazene), by nucleophilic substitution reaction. Then a post-azo coupling of p-ethylsulfonylbenzenediazonium fluoroborate or p-octylsulfonylbenzenediazonium fluoroborate toward the aniline or indole ring in P1 and P2 afforded the sulfonyl-based hromophorefunctionalized polyphosphazenes P3, P4, and P5. The polymers exhibit good solubility in common organic solvents and are thermally stable. The maximum absorption appeared at about 440nm in P3, while that of P4 was at about 393nm, which were blue-shifted about 52 and 32nm, respectively, compared to the corresponding chromophores with nitro acceptor and resulted in a wider transparency window. The poled films of P3 and P4 exhibits a resonant d33 value of 27 and 18pm/V, respectively, by second harmonic generation (SHG) measurements.

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.