RESUMO
Carbon nanothreads are a new type of one-dimensional sp3-carbon nanomaterial formed by slow compression and decompression of benzene. We report characterization of the chemical structure of 13C-enriched nanothreads by advanced quantitative, selective, and two-dimensional solid-state nuclear magnetic resonance (NMR) experiments complemented by infrared (IR) spectroscopy. The width of the NMR spectral peaks suggests that the nanothread reaction products are much more organized than amorphous carbon. In addition, there is no evidence from NMR of a second phase such as amorphous mixed sp2/sp3-carbon. Spectral editing reveals that almost all carbon atoms are bonded to one hydrogen atom, unlike in amorphous carbon but as is expected for enumerated nanothread structures. Characterization of the local bonding structure confirms the presence of pure fully saturated "degree-6" carbon nanothreads previously deduced on the basis of crystal packing considerations from diffraction and transmission electron microscopy. These fully saturated threads comprise between 20% and 45% of the sample. Furthermore, 13C-13C spin exchange experiments indicate that the length of the fully saturated regions of the threads exceeds 2.5 nm. Two-dimensional 13C-13C NMR spectra showing bonding between chemically nonequivalent sites rule out enumerated single-site thread structures such as polytwistane or tube (3,0) but are consistent with multisite degree-6 nanothreads. Approximately a third of the carbon is in "degree-4" nanothreads with isolated double bonds. The presence of doubly unsaturated degree-2 benzene polymers can be ruled out on the basis of 13C-13C NMR with spin exchange rate constants tuned by rotational resonance and 1H decoupling. A small fraction of the sample consists of aromatic rings within the threads that link sections with mostly saturated bonding. NMR provides the detailed bonding information necessary to refine solid-state organic synthesis techniques to produce pure degree-6 or degree-4 carbon nanothreads.
RESUMO
Carbon nanothreads are a new one-dimensional sp3 carbon nanomaterial. They assemble into hexagonal crystals in a room temperature, nontopochemical solid-state reaction induced by slow compression of benzene to 23 GPa. Here we show that pyridine also reacts under compression to form a well-ordered sp3 product: C5NH5 carbon nitride nanothreads. Solid pyridine has a different crystal structure from solid benzene, so the nontopochemical formation of low-dimensional crystalline solids by slow compression of small aromatics may be a general phenomenon that enables chemical design of properties. The nitrogen in the carbon nitride nanothreads may improve processability, alters photoluminescence, and is predicted to reduce the bandgap.