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

Abstract

AbstractThe zero‐dimensional polymer [Pb6(μ2OOCCH=CHFc)2(μ3‐OOCCH=CHFc)2(μ2‐η2‐OOCCH=CHFc)2(η2‐OOCCH=CHFc)2(μ4‐O)2] (1), the one‐dimensional chain polymers [Pb(η1‐μ2‐OOCCH=CHFc)2(phen)]n (phen = phenanthroline; (2), {[Cd(μ2‐η2‐OOCCH=CHFc)(η2‐OOCCH=CHFc)(H2O)2](H2O)4}n (3), and the two‐dimensional hybrid polymer {[Cd(η2‐OOCCH=CHFc)(bbbm)1.5Cl]·1.5H2O}n [bbbm = 1,1'‐(1,4‐butanediyl)bis‐1H‐benzimidazole; 4] have been prepared by the reaction of sodium β‐ferrocenylacrylate [FcCH=CHCOONa, Fc = (η5‐C5H5)Fe(η5‐C5H4)] 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 (γ) values are calculated to be 4.80 × 10–30, 5.19 × 10–30, 1.57 × 10–29, and 2.04 × 10–29 esu for 1–4, respectively. The γ values of the CdII polymers (3 and 4) are slightly larger than those of the PbII polymers (1 and 2), which indicates that the metal ions play an important role in the NLO properties of these polymers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)