A simple and effective method for the preparation of amphiphilic graphene(AG)is presented under an organic solvent-free synthetic condition.The synthetic route first involves a cyclization reaction between carboxylic groups on graphene oxide and the amino groups on 5,6-diaminopyrazine-2,3-dicarbonitrile,and subsequent reduction by hydrazine.Results of UV-vis spectroscopy,Fourier transformed infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),thermogravimetric analysis(TGA)and Raman spectroscopy have confirmed that the covalent functionalization of graphene can be achieved through the formation of imidazo[4,5-b]pyrazine on the graphene sheets.As a result,AG can be successfully dispersed in water and common organic solvents.This work successfully provides a facile and efficient way to fabricate AG and may extend the potential applications of graphene-based materials in nanoelectronic devices,polymer fillers and biological field.
Shape persistent conformations reduce the complexity of polymer materials. Herein, we propose a concept on the nanopolymer that is a nanoscale polymer chain with the repeat units of nanomonomers. In this article, a soluble organic nanopolymer of wide bandgap semiconductors was synthesized by the Yamamoto polymerization of nanogrid monomer as the repeat units with the rectangle size of ~1.7 nm × 1.2 nm. The alkyl side chain substituent at 9-position of fluorenes guarantees the polygrid with excellent solubility. Tetrafluorenes in the conjugation-interrupted backbones of polygrid acts as the active light-emitting centers without obvious green band in the fluorescence spectra of the films after 10 h annealing at 180 ℃, indicating this nanopolymer exhibits excellent spectral stability. Such soluble nanopolymers will be the fifthgeneration of macromolecular materials with a potential character of overall performance improvement.
Molecular bulks are favorable for the thermal and morphological stability in organic wide-bandgap semiconducting polymers with potential applications in both information and energy electronics. In this review, we present our progress in the design of fluorene-based bulky semiconductors with a fractal four-element pattern. Firstly, we established one-pot methods to spirofluorenes, especially spiro[fluorene-9,9′-xanthene](SFX) serving as the next-generation spiro-based semiconductors. Secondly, we observed the supramolecular forces at the bulky groups and discovered the supramolecular steric hindrance(SSH) effect on polymorphisms, nanocrystals as well as device performance. Thus, a synergistically molecular attractor-repulsor theory(SMART) was proposed for the control of nanocrystal morphology, thin film phase and morphology. Thirdly, the third possible type of defects has been identified to generate green band(g-band) emission in widebandgap semiconductors by the introduction of molecular strain design of cyclofluorene. Finally, the first bulky polydiarylfluorene with highly crystalline and β conformation was achieved by an attractor-repulsor design of tadpole-shape monomer, which offered an effective platform to fabricate stable wide-bandgap semiconducting devices. All the discoveries offer the solid basis to break through bottlenecks of organic/polymer wide-bandgap semiconductors by the improvements of overall performances.
In this study, a kind of fluorinated copolyfluorene, named poly[(4-(octyloxy)-9,9-diphenylfluorene-2,7-diyl)-alt-(2,3,5,6-tetrafluoro-1,4-phenylene)](PODPF-TFP), is synthesized by facile palladium-based direct aromatization. Compared to the non-fluorinated counterpart, poly[(4-(octyloxy)-9,9-diphenylfluorene-2,7-diyl)-alt-(p-phenylene)](PODPF-P), deeper HOMO/LUMO energy level combined with steric hindrance effect endow PODPF-TFP with excellent spectra and morphology stability. Finally, organic field-effect transistor(OFET) memory devices are fabricated with PODPF-P/PODPFTFP as the dielectric layers, and they both exhibit flash type storage characteristic. Owing to the electronegativity of fluorine atom, the device based on PODPF-TFP exhibits larger memory window and more stable I_(on)/I_(off) ratio during a retention time of 104 s as well as a better aging stability. The present study suggests that fluorinated p-n copolyfluorene electrets could enhance the capabilities of charge trapping and storage, which are promising for OFET memory devices.
Bin LiuYan BaoHai-feng LingWen-sai ZhuRui-jun GongJin-yi Lin解令海仪明东黄维
