Organometallic Nonlinear Optical (NLO) Polymers. 2. Synthesis of Main-Chain Organometallic Polymers and a Structural Study of Ferrocene NLO-Phores.

摘要

A detailed structural analysis of several ferrocene based NLO-phores were examined by X-ray diffraction. The study illustrated that electron-withdrawing groups favor and control planarity of the Pi system. Through selective functionalization of the cyclopentadienyl rings of ferrocene new monomers, were prepared in the study. One monomer was suitable for Lewis acid catalyzed transesterification-polymerization using Ti(OC4H9)4 and others were appropriate for a Knoevenagel polycondensation. The transesterification polymerization resulted in formation of an intractable polymeric material of unknown structure. The homopolymerization by the Knoevenagel technique afforded the desired polymer. The polymer was characterized by GPC and spectroscopic data. A major by-product in the polymerization was the macrocyclic lactone 10a produced from an intramolecular Knoevenagel condensation. The lactone structure was confirmed by single-crystal X-ray diffraction.