Solid-State Pathway Control via Reaction-Directing Heteroatoms: Ordered Pyridazine Nanothreads through Selective Cycloaddition

Abstract

Nanothreads are one-dimensional nanomaterials comprised of a primarily sp 3 hydrocarbon backbone. They are typically formed through cycloaddition reactions induced by compression of small molecules to high pressures. Although nanothreads have been synthesized from a range of small molecule precursors (e.g., benzene, pyridine, aniline), the ability to control reaction pathways to produce atomically precise nanothreads with distinct chemical structures remains a difficult challenge. In this study, we show how heteroatoms incorporated within starting precursors can serve as “thread directing” groups by selecting for specific cycloaddition reaction pathways. By using a less-reactive diazine group within a six-membered aromatic ring, we successfully predict and synthesize the first carbon nanothread material derived from pyridazine (1,2-diazine, C 4 H 4 N 2 ). Compared with previous nanothreads, the synthesized polypyridazine, shows a predominantly uniform chemical structure with exceptional long-range order, allowing for structural characterization using vibrational spectroscopy and X-ray diffraction. The results demonstrate how thread-directing groups can be used for precise reaction pathway control and the formation of chemically precise nanothreads with a high degree of structural order.