Syntheses, Structures, and Optical Properties of β-Ferrocenylacrylate Metal Polymers

The zero-dimensional polymer [Pb 6 (μ 2 OOCCH=CHFc) 2 -(μ 3 -OOCCH=CHFc) 2 (μ 2 -η 2 -OOCCH=CHFc) 2 (η 2 -OOCCH= CHFc) 2 (μ 4 -O) 2 ] (1), the one-dimensional chain polymers [Pb(η 1 -μ 2 -OOCCH=CHFc) 2 (Phen)] n (phen = phenanthroline; (2), j[Cd(μ 2 -η 2 -OOCCH=GHFc)(η 2 -OOCCH=CHFc)(H 2 O) 2 ]-(H 2 O) 4 ] n (3), and the two-dimensional hybrid polymer {[Cd-(η 2 -OOCCH=CHFC)(bbbm) 1 . 5 Cl].1.5H 2 O} n [bbbm = 1,1'-(1,4-butanediyl)bis-1H-benzimidazole; 4] have been prepared by the reaction of sodium β-ferrocenylacrylate [FcCH= CHCOONa, Fc = (η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )] with the appropriate metal salts. Solution-state differential pulse voltammetry for 1-4 indicated that the half-wave potentials of the ferrocenyl moieties in these polymers are all shifted to positive potential compared with that of sodium β-ferrocenylacrylate. The four polymers' third-order nonlinear optical (NLO) properties were determined by the Z-scan technique in DMF solutions. The results show that these polymers possess good nonlinear optical refraction effects. Their hyperpolarizability (y) values are calculated to be 4.80 × 10 - 3 0 , 5.19 × 10 - 3 0 , 1.57 × 10 - 2 9 , and 2.04 × 10 - 2 9 esu for 1-4, respectively. The γ values of the Cd I I polymers (3 and 4) are slightly larger than those of the Pb I I polymers (1 and 2), which indicates that the metal ions play an important role in the NLO properties of these polymers.