Polymerization of Supramolecular Diacetylenic Monomer Embedded in Porous Silicon Matrix

Abstract

We have used a porous silicon matrix filled with polydiacetylenic derivatives to obtain new nanocomposites. The polymerization, known as a topochemical process, requires optimal packing of the diacetylenic segments to allow polymerization propagation across the assembly to give a conjugated backbone. We have explored the use of intermolecular H-bond interactions between diacetylenic diacid monomers to control the polymer chain organization after the polymerization step. Resonance Raman and IRTF spectroscopy have been used to directly probe the diacetylenic segment of the monomer and the pendent side-chain arrangement. Diacetylenic derivatives have been successfully incorporated inside the pores after a specific chemical treatment to improve the filling rate of the monomer. Polarized Raman scattering indicated that the monomers have a preferential orientation along the pore axis, probably because of the confinement effect and hydrogen bonding of the self-associated carboxylic dimeric form. After the polymerization process, resonance Raman spectroscopy shows a highly oriented ene−yne backbone characterized by a blue phase.