A periodic mesoporous organosilica material functionalized with a Pd N‐heterocyclic carbene complex was synthesized by applying an electrostatic grafting method. The resulting hybrid material was characterized by solid‐state 29Si and 13C cross‐polarization magic‐angle spinning NMR spectroscopy, XRD, thermogravimetric analysis, and BET measurements. The hybrid was applied as a catalyst for the Suzuki–Miyaura cross‐coupling between aryl chlorides and phenylboronic acid under heterogeneous and aerobic conditions. The supported catalyst exhibited excellent activity and stability and it could be reused at least six times without any loss of activity. Atomic absorption spectroscopy detected no Pd contamination in the products, and leaching tests verified that the reaction was truly heterogeneous.
A thien-2-yl substituted, electron-rich phenothiazine has been converted over several steps into a redox active sol-gel precursor. Following a fluoride-catalyzed synthesis, a phenothiazine-based mesoporous hybrid organosilica was obtained. The electrochemical behavior and the luminescence properties of the immobilized chromophore have been studied using solid state fluorescence spectroscopy, electron paramagnetic resonance spectroscopy (EPR) and solid state voltammetry (CV and DPV). The influence of both the presence of fluoride anions and the acidic pH during the material synthesis were explored by means of scanning and transmission electron microscopy (SEM and TEM), X-ray powder diffraction (XRD) and nitrogen physisorption measurements. While a combination of acidic pH and fluoride was found necessary for the material formation, partial cleavage of the precursor was observed. Data obtained from both the chemical as well as the electrochemical oxidation/reduction of the immobilized PT dye indicates the formation of an organic layer containing several species inside the pore channels.
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