Synthesis Of [60] Fullerene Derivatives And Related Click Reaction

Fullerenes are fascinating carbon nanostructures with outstanding structural and functional properties. However application of fullerene is greatly limited due to the poor solubility in common solvents, low compatibility with other materials and difficulty in processing, which leads to the appearance of fullerene chemical modification. The outstanding structural and functional properties of fullerenes are critically rely on their spatial arrangements, but their strong aggregation makes them difficult to pack into ordered structures in different dimensions. The purpose of this research is to covalently link polymers and C60-in particular, using self-assemblies of polymers to manipulate C60s order and symmetry. Synthesis of fullerene polymers with high purity and well-defined structure has been difficult due to the reactive nature of fullerene towards various reaction intermediates and the often unavoidable multiple additions. To address this, a'click chemistry'approach under mild conditions has been developed, which has the advantage of simple operation as well as easy purification.Within this study, mono-addition terminal alkyne-functionalized fullerenes(Fulleryne) and terminal dialkyne-functionalized fullerenes (Fullerdiyne) derivatives were synthesized via Bingel reaction, and their reactivity of click reaction was being verified. Combined with living/controlled olymerization techniques(ATRP), polystyrene with low PDI was produced, followed by a nucleophilic addition with the end bromine replaced by nitrine group. Click reaction of Fulleryne and Fullerdiyne with PS-N3 was performed, resulting in C60 capped polystyrene and C60 connected to the junction of two polystyrene chains, respectively.Fluorine-containing C60 derivatives and fluoroalkyl-alkynyl-containing C60 derivatives were synthesized via Bingel reaction. The introduction of fluorinated segment into the C60 surface, using the special properties of fluoroalkyl chains to manipulate C60S order and symmetry. Also the fluoroalkyl-alkynyl-containing C60 derivatives can further to connect to other functional groups and polymers using click reaction. All the products were characterized by'H-NMR, 13C-NMR, FT-IR, MALDI-TOF mass spectroscopy and GPC.