Self-Assembly of Nitrogen-Rich Conjugated Metal–Organic and Organic Macrocycles

Here we report the synthesis of nitrogen-rich conjugated metal–organic and organic macrocycles that resemble truncated fragments of semiconducting 2D metal–organic and covalent organic frameworks. Key to the self-assembly of these new shape-persistent macrocycles is the development of a versatile bis(alkoxy)-tetraaminotriphenylene building block, H4TNTP-OC4, which is compatible with diverse coordination chemistry and dynamic covalent chemistry reactions. Combining H4TNTP-OC4 with nickel(II) salts leads to nickel-based metal–organic macrocycles, while reaction with tetraketones leads to pyrazine-based organic macrocycles. The fully conjugated macrocycle core supports strong interlayer stacking, out-of-plane charge transport, and well-defined nanochannels, while the macrocycle periphery provides new opportunities for atomically precise surface engineering. In particular, the nickel macrocycles display pressed pellet conductivities on the order of 10–3 S/cm and a surface area of 130 m2/g. Together, these structures show how simple macrocycles can preserve key properties of 2D crystalline frameworks while offering greater surface tunability