Abstract Polyacetylenes ( P1–P4 ) containing different stilbene groups, [(CHC) PhCHCHPhR] n (ROC m H 2m+1 ( m = 4 ( P1 ), 10 ( P2 ), 16 ( P3 )), or NO 2 ( P4 )) were designed and synthesized, respectively, using [Rh(nbd)Cl] 2 as a catalyst. Their structures and properties were characterized and evaluated by FTIR, 1 H‐NMR, 13 C‐NMR, GPC, and UV, PL, respectively. The optical limiting and nonlinear optical properties were investigated by using a frequency doubled, Q‐switched, mode‐locked Continuum ns/ps Nd:YAG laser system and their optical limiting mechanism was discussed. It is surprising to see that the stilbene pendants endow the polyacetylenes with a high thermal stability ( T d ≥ 270 °C), novel optical limiting properties and large third‐order nonlinear optical susceptibilities (up to 4.61 × 10 −10 esu). The optical limiting mechanism is mainly originated from reverse saturable absorption of molecules. In addition, it is found that the polymer with electron accepted NO 2 moiety exhibits better optical properties than that with electron donated alkoxy group because of larger π electron delocalization and dipolar effect. The strong interaction between stilbene pendants and the polyene main chain significantly results in red‐shift of fluorescence emitting peak. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4529–4541, 2008
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