Oligomerization of an ansa-ferrocene with pyrazabole bridge.

ansa-Ferrocenes with pyrazabole bridges are chemically robust entities and therefore suitable building blocks for the synthesis of rigid-rod polymers that combine redox-active Fe(II) centers and beltene-like π faces. The specific monomers we developed bear OEt groups at both tetracoordinated boron atoms (for solubility reasons) and ethynyl substituents at the 4-positions of the two pyrazole rings. Polymerization was accomplished by a condensation reaction with 1,4-diiodobenzene using a Sonogashira–Hagihara-type protocol. As a result, oligomers with a number-average molecular weight of Mn = 7.6 kDa and dispersity of Ð = 1.55 were obtained, suggesting an average chain length of about 14 repeating units based on gel permeation chromatography analysis in THF relative to narrow polystyrene standards. The molecular weight determination was complemented by MALDI-TOF mass spectrometry and (heteronuclear) NMR spectroscopy to verify the intact pyrazabole monomer repeat units and the nature of the end groups. The oligomers were further characterized by UV–vis spectroscopy and cyclic voltammetry, which demonstrated the successful synthesis of a new class of redox-active materials. [ABSTRACT FROM AUTHOR]