Simple Efficient Synthesis of Strongly Luminescent Polypyrene with Intrinsic Conductivity and High Carbon Yield by Chemical Oxidative Polymerization of Pyrene

摘要

A wholly aromatic polypyrene was synthesized by direct chemical oxidative polymerization of pyrene with ferric chloride as oxidant in hexaneitromethane. Successful synthesis of polypyrene was thoroughly confirmed by IR, UV/Vis, 1D 1H NMR, 2D 1H–1H COSY, 2D 1H–13C HSQC, MALDI-TOF MS, elemental analysis, and X-ray diffraction methods. The results indicated that the polypyrene was formed mainly through dehydro coupling between 2- or 1- and 2′- or 1′-positions on pyrene rings having a degree of polymerization of around 24. The polypyrene was purified and then separated into THF-soluble (ca. 10 %) and THF-insoluble (ca. 90 %) fractions. Compared with insulating pyrene monomer, the polypyrene is a controllably conducting polymer that has low conductivity of 3.4×10−8 S cm−1 in its virgin state, moderate conductivity of 2.28×10−4 S cm−1 upon iodine doping, but much higher conductivity of up to 81.2 S cm−1 after the insoluble polypyrene was heated up to 1300 °C in nitrogen with a high char yield of 70.6 %. In particular, the soluble polypyrene demonstrates much stronger visible color fluorescence and much lower toxicity than pyrene. The soluble polypyrene would be advantageous for detecting Fe3+ with almost no interference of other metal ions. The soluble and insoluble polypyrene fractions have potential applications as intrinsically luminescent and highly conducting carbon materials, respectively.