Fluorine‐Directed Structure‐Specific Carbon Nanothreads

Carbon nanothread (CNTh) is a sp3‐bonded one‐dimensional nanomaterial that was predicted to combine the extreme strength with excellent flexibility. However, the reported CNTh usually has a non‐uniform intrathread structure, and the synthesis of structure‐specific CNTh is still a big challenge. Here, we selecte 1,2,3‐trifluorobenzene (1,2,3‐TFB) with strong dipole as precursor. By compressing 1,2,3‐TFB to 20.1 GPa, a CNTh with a “zipper polymer” structure is obtained. Under applied pressure, 1,2,3‐TFB are anti‐parallelly stacked in column, and polymerize via selective sequential [4+2] polymerization between H‐carbon dienophile / F‐carbon dienophile and F, H‐carbon diene within the column, followed by the “zippered” bonding of the rest atoms. The obtained CNTh is highly hydrophobic with contact angle of 124.6 °. The excellent columnar anti‐parallel π∙∙∙π stacking and distinct reactivities of carbon atoms introduced by the F‐substitution are responsible for the high reaction selectivity, which provides new insight for the precise synthesis of atom‐level ordered CNThs.