The relationships between structure and nonlinear optical (NLO) properties of coordination compounds in terms of influence of molecular configuration on linear and NLO properties are reviewed. The molecular configurations involved are square pyramidal, tetrahedral, square planar, octahedral, sandwich and linear. Based on the experimental results, empirical rules of these relationships have been proposed, which may help the design of new NLO materials from organometallic and coordination compounds.

A new strategy for postfunctionalization performed on poly(N-vinylcarbazole) (PVK) has been explored to develop PVK-based nonlinear optical (NLO) polymers with a high density of chromophores and improved comprehensive properties. Thus, under the standard Vilsmeier reaction conditions, PVK is partially formylated to a high degree (up to 52% molar ratio), and these formyl groups of high reactivity are condensed with cyanoacetylated DR-1 to afford a DR-1 functionalized PVK in almost complete conversion. The Tg of the resulting polymer is 185℃, and the orientation behavior of its poled film is studied by UV-visible spectroscopy. The NLO activity, which is estimated to be 20pm/V by in situ second harmonic generation measurement, remains unchanged at 120℃ for over 1000h after a minor initial drop.

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 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.