Efficient exfoliation of graphite flakes by sonicating them in benzylamine was accomplished, affording stable suspensions of few-layers graphene. The latter were chemically modified following the Bingel reaction conditions, with the aid of microwave irradiation, producing highly functionalized graphene-based hybrid materials. The resulting hybrid materials, possessing cyclopropanated malonate units covalently grafted onto the graphene skeleton, formed stable suspensions for several days in a variety of organic solvents and were characterized by diverse and complementary spectroscopic, thermal, gravimetric, and high-resolution electron microscopy techniques. When a malonate derivative, bearing the electro-active extended tetrathiafulvalene (exTTF) moiety, was synthesized and used for the functionalization of graphene, energy dispersive X-ray (EDX) analysis verified the presence of sulfur in the corresponding graphene-based hybrid material. Moreover, the redox potentials of the exTTF-graphene hybrid material were determined by electrochemistry, while the formation of a radical ion pair that includes one-electron oxidation of exTTF and one-electron reduction of graphene was suggested with the energy gap of (graphene)•−−(exTTF)•+ being calculated as 1.23 eV.
A novel monomer incorporating the quinoline moiety as the side group was synthesized and polymerized by employing free radical as well as atom-transfer radical polymerization (ATRP) techniques. In the latter case, two different initiators were used, resulting in dibenzyloxy-or dimethylester-end-functionalized polyquinolines. All polymers were characterized primarily using 1 H NMR, gel permeation chromatography, UV-vis photoluminescence spectroscopy, and cyclic voltammetry. A systematic luminescence study was performed in different solvents and concentrations, showing that the optical properties of the newly synthesized polymers depend on both the solution's concentration and the ionic strength of the solvent. In addition, atomic force microscopy and scanning electron microscopy techniques also confirmed the close correlation between the film morphology and the solvent used for their preparation.
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