Influence of Polyfluorinated Side Chains and Soft-Template Method on the Surface Morphologies and Hydrophobic Properties of Electrodeposited Films from Fluorene Bridged Dicarbazole Monomers.

A clear case of relationship between the monomer molecular structure and the capability of tuning the morphology of electrodeposited gas bubbles template polymer thin films is shown. To this end, a series of fluorene-bridged dicarbazole derivatives containing either linear or terminally branched polyfluorinated side chains connected to the fluorene subunit were synthesized and their electrochemical properties were investigated. The new compounds underwent electrochemical polymerization over indium tin oxide electrodes to give hydrophobic films with nanostructural and morphological properties strongly dependent on the nature of the side chains. Gas bubbles templated electropolymerization was next achieved by the addition of tiny amounts of water to the monomer solutions, without using surfactants. Within the investigated set of molecules, the nanostructural properties of the soft-templated films obtained from monomers bearing linear side chains could be fine-tuned by adjusting electrochemical parameters, leading to superhydrophobic surfaces.

Improving the Electropolymerization Properties of Fluorene-Bridged Dicarbazole Monomers through Polyfluoroalkyl Side Chains.

The facile functionalization of the fluorene scaffold at the 2,7-positions was utilized to provide access to two soluble carbazole-π-carbazole derivatives CFC-H1 and CFC-F1 featuring fully hydrogenated and polyfluorinated alkyl chains at the 9-position of the fluorene π-bridging unit, respectively. The optical and electrochemical properties of the new dicarbazoles were investigated. Their electrochemical polymerization over Pt and indium tin oxide electrodes allowed the generation of electroactive polymeric films, whose physicochemical characteristics were strongly dependent on the kind of alkyl chain present on the fluorene bridge. In particular, the electropolymerization of the polyfluorinated monomer allowed the fabrication of thin films with good electrical conductivity, reversible electrochemical processes, good electrochromic properties, and enhanced water repellency with respect to its nonfluorinated analogue.

Regioselective O-Sulfonylation of N,N-Bis(2-hydroxyalkyl)tosylamides as a Synthetic Key Step to Enantiopure Morpholines.

The synthesis of enantiopure 2,6-disubstituted morpholines was realized through sequential ring opening of two different optically pure oxiranes by a tosylamide, under solid-liquid phase-transfer catalysis (SL-PTC) conditions, mono-O-sulfonylation of the resulting tosylamido-2,2'-diol, and cyclization to the morpholine. The crucial step, the regioselective formation of the monosulfonate, was controlled by taking advantage of the different stereo, electronic, and coordination properties of the oxirane-derived side chains in the diol backbone. As an application of this protocol, a new morpholine-3-carboxamide was synthesized starting from threonine.

Memory of chirality approach to the enantiodivergent synthesis of chiral benzo[d]sultams.

The "memory of chirality" stereodivergent synthesis of polyfluorobenzo[d]sultams has been developed. The interest of this protocol resides in the possibility of using the chirality of a starting sulfonamide single enantiomer to synthesize the target sultams in both absolute configurations, by using different base systems, under homogeneous conditions.