New Layered Polythiophene-Silica Composite Through the Self-Assembly and Polymerization of Thiophene-Based Silylated Molecular Precursors

Abstract

A new layered hybrid polythiophene-silica material was obtained directly by hydrolysis and polycondensation (sol-gel) of a silylated-thiophene bifunctional precursor, and its subsequent oxidative polymerization by FeCl3. This precursor was judiciously designed to guarantee its self-assembly and the formation of a lamellar polymer-silica structure, exploiting the cooperative effect between the hydrogen bonding interactions, originating from the ureido groups and the π-stacking interactions between the thiophene units. The lamellar structure of the polythiophene-silica composite was confirmed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) analyses. The solid-state nuclear magnetic resonance (NMR), UV-Vis, and photoluminescence spectra unambiguously indicate the incorporation of polythiophene into the silica matrix. Our work demonstrates that using a polymerizable silylated-thiophene precursor is an efficient approach towards the formation of nanostructured conjugated polymer-based hybrid materials.

Novel Organochlorinated Xerogels: From Microporous Materials to Ordered Domains

“…In previous studies, the formation of ordered domains in the amorphous structure of hybrid silicon xerogels was evidenced by: (i) a signal in the X-ray diffraction spectra at 2θ < 10°, (ii) the appearance in the NMR spectra of T 2,3 structures (T n , notation used for silicon atoms bonded to three oxygen atoms and Q n , for silicon atoms bonded to four bridged oxygen atoms) [ 30 , 31 ], and (iii) a band at around 1150 cm −1 in the Fourier-transform infrared spectroscopy (FTIR) spectra [ 20 , 21 , 22 ]. These observations are consistent with data obtained by mass spectrometry (MS) [ 21 ], simulations of the FTIR spectra, and inelastic neutron spectroscopy (INS).…”

Sol-Gel Chemistry: From Molecule to Functional Materials

“…Mehdi, Clément et al showed that optical properties of polythiophene embedded in a silica matrix could be controlled by polymerizing of the inorganic part of mono-silylated-thiophene precursor [8]. The crosslinking in water was assisted by self-assembly through van der Waals interactions of alkylene chains, π-stacking interactions between the thiophene units, and hydrogen bonding interactions between ureido groups.…”

Halogen-Bonded Thiophene Derivatives Prepared by Solution and/or Mechanochemical Synthesis. Evidence of N···S Chalcogen Bonds in Homo- and Cocrystals

“…Thiophene derivatives are versatile and key constituents of many organic semiconducting materials. , It has already been demonstrated that the supramolecular features of these building blocks can be translated at the macromolecular level to govern the organization of corresponding unit-containing polymers. , With this in mind, we decided to investigate the supramolecular organization of modified thiophene with the groups prone to interact by halogen bonding . Several studies have already reported the X-ray structures of halogen-bonded arrays based on brominated thiophenes at positions 2 and/or 5, along with other bromine-containing analogues .…”