The dimensional reduction of solids into smaller fragments provides a route to achieve new physical properties and gain deeper insight into the extended parent structures. Here, we report the synthesis of CuTOTP-OR (TOTP n− = 2,3,6,7tetraoxidotriphenylene), a family of copper-based macrocycles that resemble truncated fragments of the conductive twodimensional (2D) metal−organic framework Cu 3 (HHTP) 2 (HHTP = 2,3,6,7,10,. The planar metal−organic macrocycles self-assemble into ordered nanotubes with internal diameters of ∼2 nm and short interlayer distances of ∼3.20 Å. Strong π−π stacking interactions between macrocycles facilitate out-of-plane charge transport, and pressed pellet conductivities as high as 2(1) × 10 −3 S cm −1 are observed. Peripheral alkyl functionalization enhances solution processability and enables the fabrication of thin-film field-effect transistor devices. Ambipolar charge transport is observed, suggesting that similar behavior may be operative in Cu 3 (HHTP) 2 . By coupling the attractive features of metal−organic frameworks with greater processability, these macrocycles enable facile device integration and a more nuanced understanding of out-of-plane charge transport in 2D conductive metal−organic frameworks.

The percyanated dodecaborate anion [B12(CN)12]2– was prepared by reacting [B12I12]2– with CuCN in the presence of a palladium catalyst at elevated pressure and temperature in a microwave reactor. The fully cyanated cluster was isolated as a tetraethylammonium salt in yields of up to 39% and characterized by NMR and IR spectroscopy and mass spectrometry. The crystal structure of a copper complex of the percyanated anion, (CH3CN)3Cu­[μ-B12(CN)12]­Cu­(NCCH3)3, was determined by single-crystal X-ray diffraction.

Here we show how a simple change in the geometry of 1D iron–tetraoxolene chains dramatically alters the observed physical properties, including the presence of valence tautomerism, strong magnetic coupling, and electrical conductivity.