Nanoarchitecture through Strained Molecules: Cubane-derived Scaffolds and the Smallest Carbon Nanothreads

Relative to the rich library of small-molecule organics, few examples of ordered extended (i.e., nonmolecular) hydrocarbon networks are known. In particular, sp3 bonded, diamond-like materials represent appealing targets because of their desirable mechanical, thermal, and optical properties. While many covalent organic frameworks (COFs)—extended, covalently bonded, porous structures—have been realized through molecular architecture with exceptional control, the design and syn-thesis of dense, covalent extended solids has been a longstanding challenge. Here we report the preparation of a sp3-bonded, low-dimensional hydrocarbon synthesized via high-pressure, solid-state diradical polymerization of cubane (C8H8), which is a saturated, but immensely strained, cage-like molecule. Experimental measurements show that the obtained product is crystalline with three-dimensional order that appears to largely preserve the basic structural topology of the cubane molecu-lar precursor and exhibits high hardness (compara...